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1 Survey of selected phthalates

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Survey of selected phthalates Part of the LOUS-review Environmental Project No. 1541, 2014


Title:

Survey of selected phthalates

Authors and contributors:

Sonja Hagen Mikkelsen

Jakob Maag

Jesper Kjølholt

Carsten Lassen

Christian Nyander Jeppesen

Anna Juliane Clausen

COWI A/S, Denmark

Published by:

The Danish Environmental Protection Agency

Strandgade 29

1 401 Copenhagen K

Denmark

www.mst.dk/english

Year:

2014

ISBN no.

97 8-87-93026-95-7

Disclaimer:

When the occasion arises, the Danish Environmental Protection Agency will publish reports and papers concerning

research and development projects within the environmental sector, financed by study grants provided by the Danish

Env ironmental Protection Agency. It should be noted that such publications do not necessarily reflect the position or

opinion of the Danish Environmental Protection Agency.

Howev er, publication does indicate that, in the opinion of the Danish Environmental Protection Agency, the conten t

represents an important contribution to the debate surrounding Danish environmental policy.

While the information provided in this report is believed to be accurate, the Danish Environmental Protection Agency

disclaims any responsibility for possible inaccuracies or omissions and consequences that may flow from them. Neither

the Danish Environmental Protection Agency nor COWI or any individual involved in the preparation of this publication

shall be liable for any injury, loss, damage or prejudice of any kind that may be caused by persons who have acted based

on their understanding of the information contained in this publication.

Sources must be acknowledged.


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Contents

Preface ...................................................................................................................... 5

Conclusion and summary .......................................................................................... 9

Dansk resumé ......................................................................................................... 17

1. Introduction to the substance group ................................................................. 25 1 .1 Definition of the substances ............................................................................ 25 1 .2 Physical and chemical properties ...................................................................... 28 1 .3 Function of the substances for the main application areas...................................... 32

2. Regulatory framework...................................................................................... 35 2.1 Legislation................................................................................................... 35

2.1.1 Existing legislation ............................................................................ 35 2.1.2 Classification and labelling .................................................................. 40 2.1.3 REACH ........................................................................................... 42 2.1.4 Other legislation/initiatives ................................................................. 43

2.2 International agreements................................................................................ 44 2.3 Eco-labels.................................................................................................... 45 2.4 Summary and conclusions .............................................................................. 51

3. Manufacture and uses ...................................................................................... 53 3.1 Manufacturing.............................................................................................. 53

3.1.1 Manufacturing v olumes ...................................................................... 54 3.2 Import and export ......................................................................................... 57

3.2.1 Import and export of selected phthalates in Denmark ............................... 57 3.2.2 Import and export of the selected phthalates in EU................................... 58

3.3 Use ............................................................................................................ 60 3.3.1 Use in the EU ................................................................................... 60 3.3.2 Use in Denmark ................................................................................ 67

3.4 Historical trends in use .................................................................................. 7 2 3.5 Summary and conclusions .............................................................................. 7 3

4. Waste management .......................................................................................... 76 4.1 Waste from manufacture and use of selected phthalates ........................................ 7 6 4.2 Waste products from the use of selected phthalates in mixtures and articles .............. 7 6 4.3 Release of selected phthalates from waste disposal ............................................... 7 8 4.4 Summary and conclusions .............................................................................. 7 9

5. Environmental effects and exposure .................................................................80 5.1 Environmental hazard.................................................................................... 80

5.1 .1 Classification .................................................................................... 80 5.1 .2 Environmental effects ........................................................................ 81

5.2 Environmental fate........................................................................................ 83 5.3 Environmental exposure................................................................................. 84

5.3 .1 Sources of releases............................................................................. 84 5.3 .2 Monitoring data ................................................................................ 85

5.4 Environmental impact.................................................................................... 87


5.5 Summary and conclusions .............................................................................. 87

6. Human health effects ....................................................................................... 88 6.1 Human health hazard .................................................................................... 88

6.1.1 Classification .................................................................................... 88 6.1.2 DEP................................................................................................ 89 6.1.3 DIPP............................................................................................... 94 6.1.4 DPHP ............................................................................................. 95 6.1.5 DMEP ............................................................................................. 96 6.1.6 DINP and DIDP ................................................................................ 98

6.2 Human exposure..........................................................................................1 01 6.2.1 Direct exposure pathway s ................................................................. 1 02 6.2.2 Indirect exposure pathways ............................................................... 1 02

6.3 Bio-monitoring data .................................................................................... 1 04 6.4 Human health impact .................................................................................. 1 07 6.5 Summary and conclusions ............................................................................ 1 08

7. Information on alternatives.............................................................................110 7 .1 Alternatives to DINP, DIDP and DPHP use in PVC ..............................................1 10 7 .2 General features of plasticisers relevant in substitution efforts...............................1 10 7 .3 Possible plasticiser alternatives to DINP, DIDP and DPHP in PVC.......................... 1 12 7 .4 Alternatives to DEP, DMEP and DIPP .............................................................. 1 19

7 .4.1 Alternative polymers .........................................................................1 25 7 .5 Historical and future trends ...........................................................................1 25

7 .5.1 Summary and conclusions................................................................. 1 26

8. Abbreviations and acronyms .......................................................................... 128

References ............................................................................................................ 130

Appendix 1: Background information to chapter 3 on legal framework ........... 137

Appendix 2: Danish proposal on criteria for endocrine disruptors .................. 143


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Preface

Background and objectives

The Danish Environmental Protection Agency’s List of Undesirable Substances (LOUS) is intended

as a guide for enterprises. It indicates substances of concern whose use should be reduced or

eliminated completely. The first list was published in 1998 and updated versions have been

published in 2000, 2004 and 2009. The latest version, LOUS 2009 (Danish EPA, 2011) includes 40

chemical substances and groups of substances which have been documented as dangerous or which

have been identified as problematic using computer models. For inclusion in the list, substances

must fulfil several specific criteria. Besides the risk of leading to serious and long-term adverse

effects on health or the environment, only substances which are used in an industrial context in

large quantities in Denmark, i.e. ov er 100 tonnes per year, are included in the list.

Ov er the period 2012-2015 all 40 substances and substance groups on LOUS will be surveyed. The

surveys include collection of available information on the use and occurrence of the substances,

internationally and in Denmark, information on environmental and health effects, on alternatives

to the substances, on existing regulation, on monitoring and exposure, and information regarding

ongoing activities under REACH, among others.

On the basis of the surveys, the Danish EPA will assess the need for any further information,

regulation, substitution/phase out, classification and labelling, improved waste management or

increased dissemination of information.

This survey concerns selected phthalates which both attracts attention as alternatives to already

regulated phthalates such as DEHP, DBP and BBP (especially DINP, DIDP and DPHP) and are used

for other purposes (these include DEP). Certain phthalates were included in the first list in 1998

and have remained on the list since that time.

Of the selected phthalates for the survey only DMEP is included in LOUS 2009.

The entry, “Certain phthalates” in LOUS includes DMEP, DEHP, DBP, BBP and DBP. The function

of the substances is described as plasticisers in several products, primarily PVC. Of these phthalates

only DMEP is selected for the survey. Other substances included in LOUS 2009, DEHP, DBP, BBP

and DBP, are already covered by a national ban in consumer products and they are therefore not

included in the survey. Instead DEP, DIPP, DPHP, DINP and DIDP have been selected based on

either reproductive toxicity, suspected endocrine disruptive effects, or use in large tonnages.

The main reason for the inclusion of DMEP in LOUS is the classification of the substance as a

reproductive toxicant.

DEP is listed in Annex B of LOUS 2009 as part of the EU ‘Priority list of substances for further

ev aluation and their role in endocrine disruption’. However, because the registered use in Denmark

has been below 100 tonnes per year since 2001 (SPIN database) the substance is not included in

LOUS 2009.

The main objective of this study is, as mentioned, to provide background for the Danish EPA’s

consideration regarding the need for further risk management measures.


The process

The survey has been undertaken by COWI A/S (Denmark) in cooperation xx from March to October

2012. The work has been followed by an advisory group consisting of:

Shima Dobel, Danish EPA

Frank Jensen, Danish EPA

Thilde Fruergaard Astrup, Danish EPA

Bente Fabech, Danish Veterinary and Food Administration

Ulrik Heimann, The Danish Society for Nature Conservation

Hilde Balling, Danish Health and Medicines Authority

Ole Grøndahl Hansen, PVC Information Council Denmark

Jakob Zeuten, Danish Chamber of Commerce

Lone Mikkelsen, Ecological Council, Denmark

Inge Werther, DAKOFA

Cathrine Berliner Boteju, The Association of Danish Cosmetics, Toiletries, Soap and

Detergent Industries

Sonja Hagen Mikkelsen, COWI

Data collection

The survey and review is based on the available literature on the substances, information from

databases and direct inquiries to trade organisations and key market actors.

The data search included (but was not limited to) the following:

Legislation in force from Retsinformation (Danish legal information database) and EUR-Lex

(EU legislation database);

Ongoing regulatory activities under REACH and intentions listed on ECHA’s website (incl.

Registry of Intentions and Community Rolling Action Plan);

Relev ant documents regarding International agreements from HELCOM, OSPAR, the

Stockholm Convention, the PIC Conv ention, and the Basel Convention.

Data on harmonised classification (CLP) and self-classification from the C&L inventory

database on ECHAs website;

Data on ecolabels from the Danish ecolabel secretariat (Nordic Swan and EU Flower).

Pre-registered and registered substances from ECHA’s website;

Production and external trade statistics from Eurostat’s databases (Prodcom and Comext);

Export of dangerous substances from the Edexim database;

Data on production, import and export of substances in mixtures from the Danish Product

Register (confidential data, not searched via the Internet);

Date on production, import and export of substances from the Nordic Product Registers as

registered in the SPIN database;

Information from Circa on risk management options (confidential, for internal use only, not

searched via the Internet)

Monitoring data from the National Centre for Environment and Energy (DCE), the Geological

Survey for Denmark and Greenland (GEUS), the Danish Veterinary and Food Administration,

the European Food Safety Authority (EFSA) and the INIRIS database.

Waste statistics from the Danish EPA;

Chemical information from the ICIS database;

Reports, memorandums, etc. from the Danish EPA and other authorities in Denmark;

Reports published at the websites of:

The Nordic Council of Ministers, ECHA, the EU Commission, OECD, IARC, IPCS, WHO,

OSPAR, HELCOM, and the Basel Convention;

Env ironmental authorities in Norway (Klif), Sweden (KemI and Naturvårsverket),

Germany (UBA), UK (DEFRA and Environment Agency), the Netherlands (VROM,


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RIVM), Austria (UBA). Information from other EU Member States was retrieved if quoted

in identified literature.

US EPA, Agency for Toxic Substances and Disease Registry (USA) and Environment

Canada.

PubMed and Toxnet databases for identification of relevant scientific literature.

Besides, direct enquiries were sent to Danish and European trade organisations and a few key

market actors in Denmark.


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Conclusion and summary

Ov er the period 2012-2015, all 40 substances and substance groups on the Danish Environmental

Protection Agency’s List of Undesirable Substances (LOUS) will be subject to survey and review. On

the basis of the results, the Danish EPA will assess the need for any further regulation :

substitution/phase out, classification and labelling, improved waste management or increased

dissemination of information.

The selected phthalates

This survey concerns certain phthalates. The term "phthalate" is generally used to identify diesters

of ortho-phthalic acid which is an aromatic dicarboxylic acid in which the two carboxylic acid

groups are located in the ortho position in the benzene ring. The general chemical structure is

shown below where the ester side chains (R), commonly ranging from C4 to C13, may be linear,

branched or a combination of linear, branched, and ringed.

O

O

O

O

R

R

Generally both side chains are structurally identical as it is the case for the phthalates included in

the present survey, but they may differ in other phthalates. The specific characteristics affect the

phy sico/chemical and toxicological properties of the phthalate.

This review includes a survey of the following six ortho-phthalates:

A bbre-

v iation

Su bstance name EC No CA S No

DEP Diethyl phthalate 2 01-550-6 8 4-66-2

DIPP Diisopentyl phthalate 2 10-088-4 6 05-50-5

DPHP Bis(2-propylheptyl) phthalate 2 58-469-4 5 3306-54-0

DMEP Bis(2-methoxyethyl) phthalate 2 04-212-6 117-82-8

DINP *1 1 ,2-Benzenedicarboxylic acid, di-C8-10-branched alkyl

esters, C9-rich

Di-''ison onyl'' phthalate

27 1-090-9

2 49-079-5

6 8515-48-0

2 8553-12-0

DIDP *1 1 ,2-Benzenedicarboxylic acid, di-C9-11-branched alkyl

esters, C10-rich

Di-''isodecyl'' phthalate

27 1-091-4

2 47-977-1

6 8515-49-1

2 6761-40-0

Note: *1 For DINP and DIDP two CAS numbers are listed, as the “substance”, or rather mix of substances, differ

slightly depending on production process used; both numbers are addressed in much of the available literature.

1 0 Survey of selected phthalates

Regulatory framework

Harmonised classification - DIPP and DMEP are subject to harmonised CLP classification and

are classified for reproductive toxicity in category 1B. In addition DIPP is classified as acute toxic 1

in aquatic environments. Besides the harmonised classification for DIPP and DMEP, few notifiers

have self-classified DEP, DINP, and DIDP. The majority do not suggest a classification and have

indicated "data lacking" and "conclusive but not sufficient for classification".

Other EU legislation - EU legislation restricts the use of DINP and DIDP in toy s and childcare

articles which can be placed in the mouth by children and prohibits the use of DMEP and DIPP in

cosmetic products. Specific EU labelling requirements apply to certain medical devices containing

phthalates classified as reproductive toxicants in category 1 and 2. A ban on CMR substances in

concentration above the classification limits in toys also apply to DMEP and DIPP. EU also restricts

the use of DINP and DIDP in plastic materials intended to come into contact with food.

DIPP and DMEP are included in the Candidate List under the REACH Regulation and thus in the

line for being subject to the authorisation process.

Danish and other Member State legislation - Denmark has issued a national ban on the

import, sale and use of phthalates in toys and childcare articles for children aged 0 -3 years if the

products contain more than 0.05 per cent by weight of phthalates. Other national legislation

addresses the maximum concentration of phthalates in water leaving the water works and in

consumer tap water. In addition DEP has a defined occupational exposure limit. The Danish

regulation of waste sets limits for the contents of substances with classification as reprotoxic

(includes DIPP and DMEP). If the limits are exceeded the waste shall be considered as hazardous

waste and be treated as such. Denmark has specific environmental taxes on PVC plasticised with

phthalates.

The Swedish Chemicals Agency plans to investigate the need for national restriction on phthalates

toxic to reproduction or endocrine-disrupting.

International agreements - Phthalates are generally not addressed directly in international

agreements. However, hazardous wastes from production, for mulation and use of plasticisers, falls

under the provisions of the Basel Convention.

Ecolabelling schemes - Phthalates are addressed by EU and Nordic eco-labelling schemes, in

numerous product types either directly (“phthalates”, DINP, DIDP) or by means of their

classification (DIPP, DMEP and in some cases DEP).

Manufacture and use of the general plasticisers DINP, DIDP and DPHP

Manufacture - DINP is produced by four companies within the EU in Germany, Belgium and

Italy, DIDP is produced by two companies within the EU in Belgium and Italy, and DPHP is

produced in Germany and Sweden. All three substances are registered in the 100,000-1,000,000

tonnes/y band. Phthalates are not produced in Denmark.

The breakdown of the plasticiser market in Western Europe, USA and Asia is estimated as follows:

DINP/DIDP represented 63% of the plasticiser market in Western Europe in 2010, whereas it only

represented 33% of the market in the USA and 21% of the market in Asia. The total global market

for plasticisers was estimated at 6 million tonnes. Of the global plasticiser market, all phthalates

represented 84%. The on-going substitution of the traditional main general plasticiser DEHP has

not reached the same level in Asia as in Europe and the USA. Also, non-phthalate plasticiser and

“linears/other phthalates” are used to a higher extent in the USA than in Europe. According to the

European trade organisation ECPI, DINP/DIDP now (2013) represents 83% of the plasticiser

market in the EU.


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The total plasticiser content of both imported and exported articles into and out of the EU has been

estimated at about 170,000 t/y. The import of the general plasticisers DINP/DIDP (should likely be

considered as including the third key general plasticiser DPHP) in articles was estimated at

approximately 50,000 tonnes, and the export at 125,000 tonnes. Of the import into the EU, 51% of

the tonnage of the articles originates from China, whereas only 9% of the imported DINP/DIDP (on

their own) is estimated to originate from China. An overview of the extra-EU import/export by

article type is given in the report.

Application and consumption in the EU – A total breakdown of the consumption by

application in the EU of the three phthalates is not available. COWI et al. (2012) produced a best

av ailable scenario for the breakdown of the consumption by 2015 based on the available data from

industry. The major article types were wires and cables, film and sheet, flooring, and various other

coated products.

DINP, DIDP and DPHP are typically used as primary plasticisers in PVC, sometimes in combination

with other plasticisers. The actual concentrations are quite variable and depend on the desired

properties of the final PVC. Actual analyses of plasticisers in different products demonstrate that,

for the sam e product, often different combinations of plasticisers are found. The combination of

plasticisers in a PVC material is partly governed by the desired performance characteristics of the

plasticised material and partly by the desired process parameters in the manufacturing of the PVC

materials. Typical concentrations of DIDP in flexible PVC applications are reported to be around

25-50%, and the same seems to be the case for DINP.

DINP is a general plasticiser, which is applied in many products as the direct alternative for DEHP,

the formerly major general PVC plasticiser. As such DINP has a high consumption and is probably

the plasticiser which can be found in most flexible PVC products from the EU today. DINP has a

wide range of indoor and outdoor applications. DINP is a commonly used plasticiser, 95% of which

is used for flexible PVC used for construction and industrial applications, and durable goods (wire

and cable, film and sheet, flooring, hoses and tubing, footwear, toys, etc.). More than half of the

DINP used in non-PVC applications involves polymer-related uses (e.g. certain rubbers). The

remaining DINP is used in inks and pigments, certain adhesives and sealants, paints and lacquers

(where it also acts as a plasticiser) and lubricants.

DIDP is a com mon phthalate plasticiser, used primarily to soften PVC. DIDP has properties of

v olatility resistance, heat stability and electric insulation and is typically used as a plasticiser for

heat-resistant electrical cords, leather for car interiors, and PVC flooring. Non-PVC applications are

relatively small, but include use in anti-corrosion and anti-fouling paints, sealing compounds and

textile inks.

DPHP is often used as an alternative to DIDP because only minor compound changes are needed to

adapt wire formulations for example to DPHP. It is used for automotive and outdoor applications

(roofing, geo-membranes, tarpaulins, etc.). Almost all DPHP is used as a plasticiser to make PVC

soft and flexible.

Application and consumption in Denmark in 2012 of phthalates on their own was still

dominated by DEHP (C8; net import around 800-1000 tonnes /y), but with the general C9-C10

plasticisers types including DINP and DIDP/DPHP (net imports around 600 -800 tonnes/y) as a

major follow-up.

The latest available aggregate survey of annual general phthalate consumption by application for

Denmark covers 2005-2007 and is based on the revenues from the Danish environmental tax on

PVC plasticised with phthalates, in combination with other data on the application of phthalates.


The major article groups as regards phthalate consumption were wires and cables (1 .900 tonnes/y),

tubes and hoses (630 t/y), and gloves and rainwear (540 t/y).

According to the Danish Product Register DINP is clearly the major registered phthalate in

professional products marketed in Denmark, while the registered consumption of DIDP is moderate

and the consumption of the other phthalates covered is minimal, as expected. DIPP is not registered

in the Product Register. The Product Register only covers professional uses within certain criteria

and it cannot be considered to fully cover the consumption pattern in Denmark. Among others, it

does not include non-chemical articles such as wire and cable, shoe-soles, clothing, toys, etc., which

constitute major parts of the Danish consumption of phthalates. Major registered uses which can be

mentioned with respect for confidentiality are adhesives and binding agents, fillers (likely to be

understood as including sealants), paints, lacquers and varnishes. Some other dominant

applications across most substances cannot be mentioned due to confidentiality.

Manufacture and use of DIPP, DEP and DMEP

The aggregated information available on the use of DEP, DIPP and DMEP is scarce compared to

DINP and DIDP, and the few reviews available are mostly relatively old and with little information

about use and alternatives.

DIPP is registered by one company in the 100-1000 tonnes/y band (a producer of explosives

importing DIPP), and is not produced in the EU anymore. According to the registration of the

substance, DIPP is registered by a company which produces explosives as well as charges - so-called

propellants - for am munition. DIPP may also be used as plasticiser for PVC products and other

poly mers due to their similar structure and physicochemical properties, but this use is not

registered.

DEP is registered by 5 companies in the 1000-10,000 tonnes/y band; among the companies is one

of the major manufacturers of phthalates. DEP is a specialty polymer plasticiser and a solvent for

cosmetics and personal care products, among others. DEP is reported to be have been used as a

plasticizer in consumer products, including plastic packaging films, cosmetic formulations, and

toiletries, and in medical treatment tubing. Examples of uses in cosmetics and personal care

products include hair sprays, nail polishes, and perfumes, primarily as a solvent and vehicle for

fragrances and other cosmetic ingredients and as an alcohol denaturant. DEP is however not

mentioned as an accepted denaturant in EU and Danish rules from 2013 on tax exemption for

denatured alcohol. Other applications include as a camphor substitute, plasticizer in solid rocket

propellants, wetting agent, dye application agent, diluent in polysulfide dental impression, and

surface lubricant in food and pharmaceutical packaging, in preparation of pesticides. Polynt, one of

the registrants, markets DEP for the following uses: Cellulose, flavours & fragrances, cosmetics,

pharma. An anonymous source indicates current DEP use as plasticiser in EU. ECPI does not have

information of its use as a plasticiser.

DMEP is not registered under REACH and is reported not to be produced in Europe anymore.

DMEP is a specialty plasticiser which can be used in a number of polymers. The general global

applications of DMEP have included its use as a plasticiser in the production of nitrocellulose,

acetyl cellulose, PVA, PVC and polyvinylidene chloride intended for contact with food or drink.

DMEP is giving these polymeric materials good light resistance. Further, it is used as a solvent. Only

limited information regarding DMEP in consumer products in the European marketplace has been

identified. There is no information whether the substance is still in use in articles on the EU market.

Application and consumption in Denmark - Danish net imports of DEP, DIPP and DMEP is

recorded along with other phthalates in the trade statistics and the group is traded in much lower

quantities than the general plasticisers DINP and DIDP (net import of the whole group is around 90

tonnes/y).


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Waste management

The quantities of waste generated from the use of the covered phthalates as plasticisers in

production processes (formulation and conversion) are not well described. Releases to waste are

expected to occur with disposal of emptied packaging, from handling of raw materials and

intermediates, and as cut-offs in the conversion process, where the final products (articles) are

produced. For sealants, paints and non-polymer uses, the “conversion” situation includes

application on construction sites, etc. and here, a higher fraction of the material may be disposed as

waste due to the less well defined conditions.

The amounts of flexible PVC in articles subject to the Danish tax on flexible PVC with phthalates are

roughly estimated at 18,000 tonnes/year. Not all product groups containing flexible PVC are

cov ered, but the figure is deemed to include most of the flexible PVC consumption which is

plasticised with phthalates. The phthalates-containing waste fractions with biggest phthalates

contents are cable and wire, tube and hoses, gloves and rainwear, roof plates; film, sheets and tape.

The non-PVC uses of the phthalates represent much smaller phthalate amounts and at lower

phthalate concentrations.

Ranges and averages of concentrations of the general plasticisers DINP and DIDP in articles are

summarised in the report.

There are no known recycling schemes for flexible PVC in Denmark and according to the Danish

waste order, non-recycled PVC should be collected separately and be deposited. Consumers

however generally have difficulties in separating specific waste fractions, as flexible PVC is part of

many ordinary consumer products such as rainwear, boots, and packaging, for which the content of

PVC is not obv ious to the consumer. Consequently much consumer waste with flexible PVC is

deemed disposed of to municipal waste to be incinerated.

Environmental effects and exposure

None of the substances are considered to meet the criteria for classification as PBT or v PvB.

DIDP and DINP - A number of notifiers have provided self-classifications of DINP and DIDP.

About half of the notifiers have classified DINP Aquatic Acute 1 + Aquatic Chronic 1 while the other

half have classified it as Aquatic Chronic 4. DIDP has been classified Aquatic Acute 1 or Aquatic

Acute 1 + Aquatic Chronic 1 by approx. half of the notifiers and Aquatic Chronic 2 by the other half.

DIDP and DINP resemble each other much with regard to chemical structure and relevant physical -

chemical properties such as water solubility, Log Kow and sorption constants, and therefore also

with regard to effect properties and fate in the environment. As the water solubility of both

substances is very low (sub-ppb) it has only been possible to conduct tests at higher concentrations

(sub-ppm) using emulsions.

No significant acute or chronic toxic effects were observed in any tests on either of the two

substances except for a “slight but statistically significant increase in egg viability in the DINP

treated group when compared to the no treatment control” in a two-generation feeding study with

medaka (Oryzias latipes). This observation did not affect the overall conclusion by EC (2003a and

b) that DINP and DIDP are not considered to have adverse effects on the organisms (aquatic and

terrestrial) studied. With regard to possible endocrine disruption properties it was concluded that

“there is apparently no impact on any population parameter from chronic exposure to DIDP on

fish”.

The total release of DINP from waste water treatment plants to the marine areas surrounding

Denmark was estimated at around 135 kg/year.


DIPP is the only one of the phthalates in this study that has an EU harmonised environmental

classification, namely Aquatic Acute 1 (H400).

DMEP is much more water soluble and a lowest experimental acute LC50 = 56 mg/l was

determined for Daphnia magna. QSAR modelling results indicate acute LC50 for fish in the range

4.3 – 452 mg/l and a lowest chronic NOEC = 14 mg/l.

Only few environmental effect data are available on the remaining substances. However, the

av ailable data do not indicate that any of them are very toxic to aquatic organisms.

All the phthalates appear to be readily biodegradable (with DMEP as a possible exception) while

abiotic processes such as hydrolysis and photolysis do not appear to be of any significance. A BCF

(bioconcentration factor) <14.4 for DIDP in fish has been determined experimentally but is

considered to be too low. Instead the BCF = 860 for DEHP is recommended by EC (2003a and b)

for use in risk assessment.

Human health hazards and exposure

The main reason for concern in relation to phthalates and health hazards are adverse effects on the

reproductive system of in particular male animals and endocrine disruption.

DIPP and DMEP are subject to harmonised health classification and both substances are classified

for reproductive toxicity in Category 1 B. The four other phthalates selected for the study are self-

classified by industry. No classification is suggested for DPHP and only few of the notifiers have

self-classified DEP, DINP, and DIDP based on a number of adverse effects. The reason for not

classifying the substances is typically lack of sufficient data.

The six phthalates are generally of low acute toxicity via all routes and with low skin and eye

irritation potential. There are case reports referring to skin sensitisation to plastic articles in

patients with dermatitis, e.g. in relation to DEP, but in general phthalates are not considered

sensitising. Of the selected phthalates, DEP has been evaluated against the proposed Danish criteria

for endocrine disrupters as a suspected endocrine disrupter in category 2a. The Danish EPA has

suggested that also DINP be ev aluated against agreed criteria for endocrine disruption.

No significant exposure to DMEP is expected as the substance is not registered for use in the EU.

DEP has not been identified as an ingredient in cosmetic and personal care products in Denmark

but may be imported from other countries and an exposure of DEP could therefore happen .

Occupational exposure is primarily expected via dermal contact in relation to handling of flexible

PVC products, formulation and use of sealants and paints, and contact with cosmetics and personal

care products. Direct consumer exposure is expected from dermal contact with various flexible PVC

products, wires and cables and in particular imported cosmetics and personal care products.

Indirect exposure of consumers occurs in relation to the indoor climate via dust and air.

In a newly published study with r esults from human biomonitoring on a European scale, all 17

participating countries analysed among others metabolites of some phthalates including DEP,

DINP, and DIDP, in urine. Samples were taken from children aged 6 -11 years and their mothers

aged 45 years and under. The results showed higher levels in children compared to mothers, with

the exception of MEP which is not regulated and is mainly used in cosmetics. A possible explanation

is children’s relatively higher exposure: they are more exposed to dust, playing nearer the ground,

and have more frequent hand-to- mouth contact; and they eat more than adults in relation to their

weight. Consumption of convenience food, use of personal care products and indoor exposure to

v inyl floors and wallpaper have all been linked to higher phthalate levels in urine.


15

DINP and DIDP have been reviewed by ECHA in relation to the ban of these two phthalates in toys

and childcare articles (entry 52 in Annex XVII to REACH). It was concluded that a risk from the

mouthing of toy s and childcare articles with DINP and DIDP cannot be excluded if the existing

restriction were lifted. No further risks were identified. These conclusions were supported by

ECHA’s Committee for Risk Assessment.

The ECHA review also addressed the need for considering combined effects of phthalates and other

substances with same mode of action in the risk assessment of the substances, e.g. in relation to

antiandrogenic properties.

Alternatives

When considering the possibilities for substitution of specific plasticisers, it is important to note

that a vast number of organic substances can act as plasticisers in polymers. Contrary to many other

substitution efforts, plasticising is not dependent on highly specific chemical bonding, but rather on

a series of characteristics which the plasticiser must have to meet functional demands. Finding the

good plasticiser is therefore not a distinct theoretical science, but rather an empiric process

supported by a large number of measuring methods designed for this pu rpose.

Many families of plasticisers are available. Most of them have however certain chemical

functionalities in common with the phthalates family. They are typically branched, quite

"v oluminous" molecules, with many oxygen bonds (= carbonyl groups). Many have benzyl rings or

the hydrogenated counterpart, cyclohexane.

DINP, DIDP and DPHP - Most av ailable information on alternatives to primary plasticisers like

DINP, DIDP and DPHP has been reviewed as part of the search for substitutes for the classic

general plasticiser DEHP (to which DINP and to as lesser extend DIDP and DPHP are the key

alternatives today). Several alternatives are however available, both ortho-phthalates (with basic

structure similar to DINP, DIDP and DPHP), tere-phthalates and non-phthalate plasticisers. The

one non-ortho-phthalate with the widest coverage for traditional DEHP applications is likely its

terephthalate counterpart DEHT, which has the same chemical composition, but a different form,

and therefore different environmental characteristics. No single non-orthophthalate plasticiser

seems to be identified which covers all traditional applications of DEHP (and thus DINP, its main

alternative). Together, however, the reviewed non-orthophthalates cover most or all the key

applications. The non-orthophthalate alternatives best described include: DINCH, ASE, DGD,

DEGD (in mixtures), COMGHA, DINA, ATBC and GTA. While most of these have their own

env ironmental issues, many of them are deemed to have overall better environmental performance

than DEHP based on the available information. A direct environment and health comparison of

DINP, DIDP and DPHP and their alternatives has not been found.

DEP, DIPP and DMEP - A wide search of alternatives to the phthalates DEP, DIPP and DMEP

has not been possible within this project. For DEP’s use as a denaturant, many alternatives exist,

and DEP is not a part of the 2013 list of denaturants accepted for attaining exemptions from alcohol

tax in EU Member States (including Denmark). Based on a 2010 review of alternatives to DEHP,

DBP and BBP, there are clear indications that non -orthophthalate alternatives to key applications of

DEP, DIPP and DMEP are available. Examples include GTA, ATBC, COMGHA, DINCH, DINA,

DGD, ASE and a mix with DEGD as a major component.

Alternative materials - Focusing on alternative materials with characteristics similar to the

characteristics of flexible PVC, the following flexible polymers are among the principal alternatives

to flexible PVC (Maag et al., 2010): Ethylene vinyl acetate (EVA), Low density polyethylene (LDPE),

poly olefin elastomers, polyurethanes (may in some cases be plasticised with phthalates), isobutyl

rubber, EPDM rubber (may in some cases be plasticised with phthalates) and silicone rubber.


Data gaps

In summary, the use of the general plasticisers DINP and DIDP is well described, even an actual

distribution on end-products is not available for Denmark. DPHP is less well described, but has

functional characteristics similar to DIDP and can be used as an alternative to DIDP. As regards

DEP, the registered tonnages and other information indicate that it still has a significant use in the

EU, but more details about the use are needed. DIPP seem to have a very narrow application range

in the EU, and it is questionable if much more information can be found. DMEP is still not

registered, indicating that its future use in the EU may be v ery limited or absent.

In conclusion, the following major data gaps are identified:

More specific information on the consumption of DINP, DIDP, DPHP and DEP by application

with special focus on DINP and DEP due to their human health characteristics.

Inv estigation of the fate of plasticised PVC waste in Denmark, including collection rates, for

both consumer waste and waste from professionals.

Information on direct alternatives to DEP by major applications, in view of its significant

production range and related exposure potential .

Direct comparisons of DINP, DIDP and DPHP with available alternatives for relevant

applications.

Identification of the most important metabolites to be used as a biomarker for human

exposures.

Limited information on endocrine specific end-points for some phthalates

Further documentation of the effects of cumulative exposure to e.g. antiandrogenic and

estrogenic substances at different levels.


17

Dansk resumé

I perioden 2012-2015 vil alle 40 stoffer og stofgrupper på Miljøstyrelsens liste ov er uønskede stoffer

(LOUS) bliv e kortlagt, og Miljøstyrelsen vil på grundlag af resultaterne vurdere behovet for

y derligere regulering, substitution/udfasning, klassificering og mærkning, forbedret

affaldshåndtering eller øget udbredelse af information.

De udvalgte ftalater

Denne undersøgelse vedrører udvalgte ftalater. Ordet ftalat bruges i almindelighed om diestre af

ortho-ftalsyre, som er en aromatisk dicarboxylsyre hvori de to carboxylsyregrupper sidder i ortho

positionen på benzenringen, dvs. lige ved siden af hinanden. Den generelle struktur for ortho-

ftalater er vist nedenfor, hvor ester sidegrenene (R) – normalt C4-C13 – kan være lineære eller

forgrenede, evt. også med yderligere ringstrukturer.

O

O

O

O

R

R

I de fleste tilfælde er sidegrenene identiske, hvilket er tilfældet for ftalaterne omfattet af dette

studie, men de kan være forskellige. Den specifikke sammensætning af stoffet påvirker dets fysisk-

kemiske og toksikologiske egenskaber.

Denne kortlægning omhandler følgende seks ortho-ftalater:

Forkor

t else

St ofnavn EC Nr CA S Nr

DEP Diethylftalat 2 01-550-6 8 4-66-2

DIPP Diisopentylftalat 2 10-088-4 6 05-50-5

DPHP Bis(2-propylheptyl)ftalat 2 58-469-4 5 3306-54-0

DMEP Bis(2-methoxyethyl)ftalat 2 04-212-6 117-82-8

DINP

*1

1 ,2-Benzendicarboxylsyre, di-C8-10-forgrenede alkyl estre,

C9 -rige

Di-''ison onyl'' ftalat

27 1-090-9

2 49-079-5

6 8515-48-0

2 8553-12-0

DIDP

*1

1 ,2-Benzendicarboxylsyre, di-C9-11- forgrenede alkyl estre,

C10-rige

Di-''isodecyl'' ftalat

27 1-091-4

2 47-977-1

6 8515-49-1

2 6761-40-0

Note: *1 DINP og DIDP har hver to CAS numre, da “stoffet”, eller rettere stofbladingen er lidt forskellig

a fhængig af hvilken proces, der er brugt ved dets produktion. Begge numre er brugt i megen af den tilgængelige

lit teratur.


Regulering

Der er v edtaget harmoniserede klassifikationer for DIPP (Reprotoxic 1B; H360FD and Aquatic

Acute; H400) og DMEP (Reprotoxic 1B; H360Df).

Foruden den harmoniserede klassificeringer af DIPP og DMEP er der udført selv -klassificering for

en række effekter for DEP, DINP og DIDP af et mindretal af anmelderne. Mange anmeldere har

angivet, at data ikke er tilstrækkelige til en klassificering, som årsag til at stofferne er notificeret

uden klassificering.

Ifølge EU lov givningen er anvendelsen af DINP og DIDP i legetøj og artikler til børnepleje, der kan

tages i munden, samt i plastik anvendt til fødevarekontakt begrænset og DMEP og DIPP er forbudt i

kosmetiske produkter. Der er særlige mærkningskrav for visse typer medicinsk udstyr, som

indeholder ftalater, der er klassificerede som toksiske for reproduktionen i kategori 1 og 2, dvs.

DMEP og DIPP. Et forbud mod CMR-stoffer i legetøj i koncentrationer over klassificeringsgrænsen

omfatter også DMEP og DIPP.

I Danmark er der forbud mod import, salg og anvendelse af legetøj og børneartikler, som

indeholder mere end 0,05 vægt-% ftalater, til børn under 3 år. Anden regulering sætter grænser for

afløbsv and fra spildevandsrensningsanlæg og drikkevand. For DEP, DINP og DIDP er der etableret

grænseværdier for arbejdsmiljøet. Affaldsbekendtgørelsen sætter grænser for indhold af stoffer, der

er klassificeret som skadelige for reproduktionen (det gælder her DMEP og DIPP). Affald med

højere indhold er defineret som farligt affald og skal behandles derefter. Danmark har særlige

afgifter på PVC blødgjort med ftalater.

DIPP og DMEP anses som særlig problematiske stoffer (SVHC) og er optaget på Kandidatlisten

under REACH reguleringen.

Den sv enske Kemikalieinspektion har planer om at undersøge behovet for national regulering af

ftalater, der er toksiske for reproduktionen eller har hormon -forstyrrende effekter.

Internationale aftaler - Ftalater er generelt ikke nævnt direkte i internationale miljøaftaler. Farligt

affald fra produktion, formulering og anvendelse af plastik er dog omfattet at Basel konventionen.

Miljømærkning - Brug af ftalater, eller enkeltstoffer herunder, er ikke tilladt i en lang række

produkttyper omfattet af det nordiske Svanemærke og EU Blomsten. Ftalater (som stofgruppe),

DINP og DIDP er direkte nævnt i mærkningskriterierne for mange af disse produkttyper, mens

DIPP, DMEP og i v isse tilfælde DEP er omfattet via deres klassificering.

Fremstilling og anvendelse

Der produceres ikke ftalater i Danmark, men EU som helhed er en stor eksportør af (ortho-)

ftalater.

Fremstilling og anvendelse af de generelle blødgørere DINP, DIDP og DPHP

DINP producers af 4 virksomheder i EU i Ty skland, Belgien og Italien, DIDP producers af 2

v irksomheder i EU i Belgien og Italien, mens DPHP fremstilles i Tyskland og i Sverige. Alle 3

stoffer er registreret i 1 00.000-1.000.000 tons/år intervallet.

Fordelingen af blødgører-markedet i Vesteuropa, USA og Asien er anslået som følger af

en af kilderne på området: DINP/DIDP repræsenterede i 2010 63% af blødgører-markedet i

Vesteuropa, mens det kun udgjorde 33% i USA og 21% i Asien. The globale blødgører-marked

udgjorde i alt ca. 6 millioner tons, hvoraf ftalater udgjorde 84%. Den igangværende substitution af

DEHP har ikke nået samme niveau i Asien som i Europa og USA. Desuden anvendes ikke-ftalat


19

blødgørere samt ”lineære/andre ftalater” i højere grad i USA end i Europa. Det skal bemærkes, at

ifølge ECPI repræsenterer DINP/DIDP nu 83% af markedet i EU.

Dansk netto-import i 2012 af ftalater (stofferne alene) var fortsat domineret af DEHP (C8, netto-

import 800-1000 t/år), men med C9-C10 blødgørerne (DINP-DIDP/DPHP) på en andenplads

(600-800 t/år).

Det totale blødgører-indhold i henholdsvis importerede og eksporterede artikler ind og ud af EU er

anslået til omkring 170.000 t/år. Importen af de generelle blødgørere DINP/DIDP (skal i dag nok

opfattes som inkluderende DPHP) i artikler er blevet anslået til omkring 50.000 t/år, mens

eksporten var ca. 125.000 t/år. Af importen ind i EU kom 51% af vare-tonnagen fra Kina, mens kun

9% af importen af DINP/DIDP (som stofferne) kom fra Kina. En oversigt over EU import og eksport

per artike type er vist i rapporten.

DINP, DIDP og DPHP anvendes typisk som primære blødgørere i PVC, somme tider i

kombination med andre blødgørere. De konkrete koncentrationer varierer en del og afhænger af

hv ilke egenskaber, der ønskes for den færdige PVC blanding. Kemiske analyser viser, at selv for den

samme produkttype kan der findes forskellige kombinationer af blødgørere. Typiske DIDP

koncentrationer angives at være 25-50 vægt-%, og det samme synes at være tilfældet for DINP.

DINP er en generel blødgører, der anvendes i mange produkter, som det direkte alternativ til

DEHP, der tidligere var den dominerende blødgører. Der er således et stort forbrug af DINP og

denne blødgører er nok den, der kan findes i de fleste PVC-produkter produceret i EU i dag. DINP

anvendes således i en lang række sammenhænge både indendørs og udendørs. 95% af forbruget

anvendes til blødgøring i byggeri og industri, herunder varer som kabler og ledninger, film og ark,

gulvbelægning, rør og slanger, fodtøj, legetøj med mere. Mere end halvdelen af den DINP, der ikke

anvendes til blød PVC, bliver brugt til andre polymerer (for eksempel visse gummityper). Resten

anvendes i blæk, pigmenter, visse lime og fugemasser, maling og lak (hvor den også fungerer som

blødgører) og i smøremidler.

DIDP er en almindelig blødgører, der hovedsageligt anvendes til PVC. DIDP er modstandsdygtig

ov erfor fordampning og varme og den anvendes typisk som blødgører i el -ledninger, betræk i biler

samt PVC-gulvbelægning. Andre anvendelser end til PVC er relativt begrænsede, men omfatter anti-

korrosions- og antifouling maling, fugemasser og blæk til tekstiler.

DPHP anvendes ofte som alternativ til DIDP, fordi kun mindre ændringer i PVC-formuleringerne

er nødv endige, for eksempel til el-ledninger. DPHP bruges til biler og udendørsanvendelser

(tagmembraner, geo-membraner, presenninger mv.). Næsten al DPHP anvendes til blød PVC.

Et fuldt overblik ov er forbruget af disse tre ftalater opdelt efter anvendelse findes ikke. COWI

et al. (2012) udarbejdede dog et ov erslags-scenarie for forbrugsfordelingen baseret på tilgængelige

data fra industrien. De v æsentligste artikel-typer var el ledninger og kabler, film og ark,

gulvbelægninger samt en række andre coatede produkter.

Den seneste tilgængelige oversigt over det generelle årlige ftalatforbrug fordelt på anvendelser i

Danmark er fra 2005-2007 og er baseret på den indkomne miljøafgift på ftalatholdige PVC

produkter, i kombination med andre data om anvendelsen af ftalater. De største artikelgrupper

hv ad angår ftalatforbrug var el-ledninger og kabler (1.900 t ftalater/år), rør og slanger (630 t/år) og

handsker og regntøj (540 t/år).

Ifølge det danske Produktregister er DINP er helt klart den væsentligste ftalat i professionelle

produkter, der markedsføres i Danmark, mens det registrerede forbrug af DIDP er moderat, og

forbruget af de andre udvalgte ftalater som forventet er minimalt. DIPP er ikke registreret i


Produktregistret. Produktregistret dækker kun erhvervsmæssig brug inden for visse kriterier, og det

kan ikke anses for fuldt ud at dække forbruget i Danmark. Blandt andet omfatter det ikke artikler

såsom ledninger og kabler , skosåler , tøj, legetøj osv., der udgør væsentlige dele af det danske

forbrug af ftalater. Større registrerede anvendelser, der kan nævnes uden at krænke fortroligheden,

er lim og bindemidler, fyldstoffer (formentlig omfattende fugemasser), maling, lak og fernis. Andre

v igtige anvendelser kan ikke nævnes på grund af fortrolighed.

Fremstilling og anvendelse af DEP, DIPP og DMEP

DIPP er registret af én virksomhed i 100-1.000 t/år intervallet (en producent af sprængstoffer, der

importerer DIPP), og produceres ikke i EU mere. DEP er registreret af fem virksomheder i 1 .000-

1 0.000 t/år intervallet. Blandt virksomhederne er en af de større producenter af ftalater. DMEP er

ikke registreret og det angives at den ikke producers mere i EU.

Dansk netto-import af DEP, DIPP og DMEP er opgjort sammen med andre ftalater i

udenrigsstatistikken og den gruppe handles i meget lavere mængder end de generelle blødgørere

DINP/DIDP (netto-importen af hele stofgruppen er ca. 90 t/år).

Den eksisterende sammenfattede information om anvendelsen af DEP, DIPP og DMEP er sparsom

sammenlignet med DINP og DIDP, og de få eksisterende sammenfatninger er for det meste relativt

gamle og kun med lidt information om anvendelser og alternativer.

DEP er en specialblødgører til polymerer og et opløsningsmiddel til kosmetik og produkter til

personlig pleje. DEP er tidligere anvendt som blødgører i forbrugerprodukter såsom pakkefilm af

plast, kosmetik blandinger, toiletartikler og i m edicinske slanger. Eksempler på kosmetik og

personlige plejeprodukter er hårspray, neglelak og parfumer, hvor det kan være anvendt som

opløsningsmiddel, som bærer af duftstoffer og til denaturering af alkohol. DEP er imidlertid ikke

nævnt blandt de stoffer , der i EU og Danmark fra 2013 er accepteret som denatureringsmidler, der

giv er fritagelse for nationale alkoholafgifter. En anonym kilde indikerer, at DEP aktuelt anvendes

som blødgører i EU. ECPI har ikke kendskab til en anvendelse af DEP som blødgører. Andre nævnte

anvendelser er som alternativ til kamfer, som blødgører i ladninger i ammunition, slipmiddel,

hjælpestof til indfarvning, opløsningsmiddel i tandaftryk af polysulfider, overflademiddel til

pakninger af fødevarer og farmakologiske produkter, samt til fremstilling af pesticider. Polynt, en af

registranterne, markedsfører DEP til følgende anvendelser: Cellulose, smags- og duftstoffer,

kosmetik og farmakologi.

DIPP er registreret af en producent af sprængstoffer og ladninger – såkaldte drivmidler

(”propellants”) – til ammunition. DIPP kan muligvis også anvendes som blødgører i PVC og andre

poly merer i kraft af dets lighed i struktur og fysisk-kemiske egenskaber, men denne anvendelse er

ikke registret.

DMEP er en specialblødgører, som kan anvendes i en række polymerer. DMEP har globalt set

blandt andet været brugt som blødgører i produktion af nitrocellulose, acetyl cellulose, PVA, PVC og

poly vinylidenklorid til fødevarekontakt og drikkevarer. DMEP giver disse polymermaterialer god

ly sresistens. Det er desuden anvendt som opløsningsmiddel. Kun meget begrænset information om

DMEP i forbrugerprodukter på det europæiske marked er fundet. Der er ingen information om,

hv orvidt dette stof stadig anvendes på det europæiske marked.

Ifølge det Danske Produktregister er DINP klart den mest anvendte ftalat i produkter til

professionelle på det danske marked, mens det registrerede forbrug af DIDP er moderat og

forbruget af de andre omfattede ftalater er marginalt, som forventet. DIPP er ikke registreret i

Produktregisteret. Produktregisteret dækker kun professionelle anvendelser indenfor visse

kriterier, og det kan ikke anses som dækkende for det danske forbrugsmønster. Blandt andet er

sådanne ikke-kemiske artikler som ledninger og kabler, skosåler, tøj, legetøj, osv., som udgør store


21

dele af det danske forbrug af ftalater, ikke dækket. Væsentlige registrerede, ikke-fortrolige

anvendelser er lime og bindemidler, spartelmasser (sandsynligvis skal det opfattes som også

omfattende fugemasser), maling og lak. Visse større anvendelser på tværs af de fleste af stofferne

kan ikke nævnes på grund af krav om fortrolighed.

Affaldshåndtering

Mængderne af affald, der frembringes fra brug af stofferne som blødgørere i produktionsprocesser

(formulering og konvertering), er ikke velbeskrevet. Affald forventes at frembringes ved

bortskaffelse af tømt emballage, fra håndtering af råmaterialer og intermediære forbindelser og som

afskær i konverteringsprocessen, hvor slutprodukterne fremstilles. For fugemasser, maling og visse

ikke-polymere anvendelser sker ”konverteringen” på byggepladser med videre, og her kan større

andele af materialet gå tabt som affald på grund af de mindre veldefinerede forhold.

Mængden af blød PVC i artikler som er underlagt dansk afgift på ftalater i blød PVC er groft anslået

til 1 8.000 t/år. Ikke alle varegrupper med indhold af blød PVC er dækket af opgørelsen, men denne

mængde anses for at dække størstedelen af forbruget af PVC blødgjort med ftalater. De ftalatholdige

affaldsfraktioner, der repræsenterede de største ftalatindhold, var ledninger og kabler, rør og

slanger, handsker og regntøj, tagplader, film og ark samt tape. Andre anvendelser af ftalaterne end

PVC udgjorde langt mindre mængder ftalater og i lavere ftalatkoncentrationer. Intervaller og

gennemsnit for koncentrationer af de generelle blødgørere DINP og DIDP i artikler er opsummeret i

rapporten.

Der findes ikke genanvendelsesordninger for blød PV C i Danmark og ifølge Affaldsbekendtgørelsen

skal PVC, der ikke genanvendes, indsamles separat og deponeres. Forbrugerne har imidlertid

generelt svært ved at separere specifikke affaldsfraktioner da blød PVC er en del af mange

almindelige forbrugerprodukter som regntøj, støvler, indpakning, osv ., hvori indholdet af PVC ikke

indlysende. Det vurderes derfor, at meget affald med blød PVC går til affaldsforbrænding.

Miljøeffekter og eksponering

DIPP er den eneste ftalat i dette studie, der har en harmoniseret miljøklassifikation, nemlig

Aquatic Acute 1 (H400). En række anmeldere har angivet selvklassifikation for DINP og DIDP.

DINP er af ca. halvdelen af anmelderne klassificeret som Aquatic Acute 1 plus Aquatic Cronic 1,

mens den anden halvdel har klassificeret den som Aquatic Cronic 4. DIDP er klassificeret Akvatisk

Akut 1 eller Akvatisk Akut 1 + Akvatisk Kronisk 1 af ca. halvdelen af anmelderne og Akvatisk

Kronisk 2 af den anden halvdel.

DIDP og DINP ligner hinanden meget hvad angår kemisk struktur og relevante fysisk-kemiske

egenskaber såsom vandopløselighed, Log Kow og adsorptionskonstanter, og derfor også hvad angår

effekter og skæbne i miljøet. Da vandoplyseligheden af begge stoffer er meget lav (under pbb-

niv eau) har det kun været muligt at teste højere koncentrationer (under ppm niveau) ved hjælp af

emulsioner.

Ingen signifikante akutte eller kroniske effekter blev observeret i nogen tests af de to stoffer,

undtagen en ”lille men statistisk signifikant stigning i ægs overlevelsesevne i den DINP-behandlede

gruppe ved sammenligning med kontrolgruppen” i et to-generations madningsforsøg med medaka

(Oryzias latipes; japansk risfisk). Denne observation påvirkede ikke hovedkonklusionen i EU's

risikovurdering af stofferne (EC, 2003a og b) at DINP og DIDP ikke anses for at have negative

effekter på de studerede organismer (akvatiske og terrestriske). Med hensyn til hormonlignende

egenskaber blev det konkluderet, at “der er tilsyneladende ingen påvirkning af

populationsparametre ved kronisk eksponering af fisk med DIDP".

Det totale udslip af DINP fra spildevandrensningsanlæg til havområderne der omgiver Danmark er

anslået til omkring 135 kg/år.


DMEP er meget mere vandoplyselig og en lavest eksperimentel akut LC50 for fisk på 56 mg/l blev

fundet for Daphnia magna. QSAR model resultater indikerer en akut LC50 for fisk i intervallet 4.3

– 452 mg/l og en laveste kronisk NOEC på 14 mg/l.

Kun få miljøeffektdata er tilgængelige for de øv rige stoffer. De tilgængelige data indikerer dog ikke

at nogen af dem er meget giftige for vandlevende organismer.

Alle de omfattede ftalater lader til at være let bionedbrydelige (med DMEP som en mulig

undtagelse) mens abiotiske processer såsom hydrolyse og fotolyse tilsyneladende ikke har nogen

v idere betydning. En BCF på <14,4 for DIDP in fisk er blevet fastlagt eksperimentelt, men anses

som v ærende for lav. I stedet er BCF’en = 860 for DEHP anbefalet af EC (2003a and b) til brug i

risikovurderinger.

Ingen af de omfattede stoffer anses for at opfylde kriterierne for klassifikation som PBT eller vPvB.

Humantoksiske effekter

Den v æsentligste årsag til bekymring i forhold til ftalater er stoffernes påvirkning af reproduktionen

hos især hanner og mistanke om hormonforstyrrende effekter.

DIPP og DMEP har begge en harmoniseret klassificering for reproduktionstoksicitet i kategori 1B.

De fire andre ftalater udvalgt til undersøgelsen er selvklassificeret af industrien. Der er ikke

foreslået nogen klassificering af DPHP og kun få af anmeldere har selvklassificeret DEP , DINP og

DIDP. Årsagen er angivet som mangel på tilstrækkelige data.

De seks ftalater har generelt lav akut toksicitet via alle eksponeringsveje og begrænset potentiale for

hud-og øjenirritation. Der findes case-rapporter, der viser hudsensibilisering ov er for plastartikler

hos patienter med dermatitis, fx i forhold til DEP, men generelt ftalater anses ikke sensibiliserende .

Af de udv algte ftalater er DEP blevet evalueret i forhold til de foreslåede danske kriterier for

hormonforstyrrende effekter, som mistænkt hormonforstyrrende i kategori 2a. Den danske

Miljøstyrelse har foreslået, at også DINP blive evalueret i forhold til vedtagne kriterier for

hormonforstyrrende effekter.

Der forv entes ikke nogen væsentlig eksponering for DMEP, da stoffet ikke er registreret til brug i

EU. DEP er ikke blevet identificeret som en ingrediens i kosmetiske produkter i Danmark, men

eksponering kan forekomme i forbindelse med importerede produkter.

Erhvervsmæssig eksponering forventes primært via hudkontakt i relation til håndtering af

produkter af blød PVC, formulering og anvendelse af fugemasse og maling, og kontakt med

kosmetik og produkter til personlig pleje. Direkte forbrugereksponering forventes fra hudkontakt

med forskellige fleksible PVC-produkter, ledninger og kabler og især importeret kosmetik og

produkter til personlig pleje . Indirekte eksponering af forbrugerne sker i forhold til i ndeklimaet via

støv og luft .

I en nyligt offentliggjort undersøgelse med resultater fra human biomonitering på europæisk plan,

analyserede alle 17 deltagerlande blandt andet metabolitter af visse ftalater i urin, herunder DEP ,

DINP og DIDP. Prøv erne blev taget fra børn i alderen 6 -11 år og deres mødre i alderen 45 år og

derunder. Resultaterne viste højere niveauer i børn i forhold til deres mødre , med undtagelse af

MEP, metabolit af DEP, som ikke er reguleret , og hovedsagelig anvendes i kosmetik . En m ulig

forklaring er børns relativt højere eksponering: de er mere udsat for støv , leger tæt ved jorden, og

har hyppigere hånd-til- mund-kontakt , og de spiser mere end voksne i forhold til deres vægt.

Indtag af føde, brug af produkter til personlig pleje og indendørs eksponering for vinylgulve og tapet

er alle blevet forbundet med højere ftalat-niveauer i urinen.


23

DINP og DIDP er blev et vurderet af ECHA i forbindelse med forbud mod disse to phthalater i

legetøj og småbørnsartikler (artikel 52 i bilag XVII til REACH). Det blev konkluderet, at en risiko

forbundet med at sutte på legetøj og småbørnsartikler med DINP og DIDP ikke kan udelukkes, hvis

den eksisterende begrænsning blev ophævet. Ingen yderligere risici blev identificeret. Disse

konklusioner blev støttet af ECHAs udvalg for risikovurdering.

Behov et for at ov erveje kombinationseffekter af phthalater og andre stoffer med samme

v irkningsmekanisme i risikovurderingen af stofferne, fx i forhold til antiandrogene egenskaber , blev

også fremhævet.

Alternativer

Ved v urdering af mulighederne for substitution af specifikke blødgørere, er det vigtigt at notere sig,

at et stort antal organiske stoffer kan fungere som blødgørere i polymerer. I modsætning til mange

andre forsøg på substituering er blødgøring ikke a fhængig af helt specifikke kemiske bindinger, men

snarere af en række karakteristika som blødgøreren må have, for at opnå de krævede egenskaber. At

finde den rette blødgører er således ikke en distinkt teoretisk videnskab, men snarere en empirisk

proces støttet af et stort antal målemetoder, der er designet til formålet.

Mange mulige familier af blødgørere er til rådighed. De fleste af dem har imidlertid visse kemiske

funktionaliteter til fælles med ftalatfamilien. De er typisk forgrenede, ret ”voluminøse” molekyler

med mange iltbindinger (= carbonylgrupper). Mange indeholder benzylringe eller deres

hy drogenerede sidestykke, cyclohexan.

De fleste af de tilgængelige oplysninger om alternativer til primære blødgørere som DINP, DIDP

og DPHP er blev et gennemgået som led i søgen efter alternativer til den klassiske generelle

blødgører DEHP (for hvilken DINP og i mindre grad DIDP og DPHP er hov edalternativerne i dag).

Adskillige alternativer er imidlertid til rådighed, både ortho-ftalater (med samme grundlæggende

struktur som DINP, DIDP og DPHP), tere-ftalater og andre stoffer end ftalater. Af stoffer der ikke er

ortho-ftalater dækker DEHP’s tere-ftaliske sidestykke DEHT den største del af de traditionelle

DEHP-anv endelser. DEHT har den samme kemiske sammensætning som DEHP, men en anden

form og derfor andre miljøegenskaber. Der ud over synes der ikke at være identificeret nogen enkelt

ikke-ftalat, der dækker alle traditionelle anvendelser af DEHP (og dermed DINP, dens

hov eralternativ). Tilsammen dækker de gennemgåede ikke-ortho-ftalater dog de fleste eller alle

hov edanvendelser. De bedst beskrevne ikke-ortho-ftalat alternativer er, foruden DEHT, DINCH,

ASE, DGD, DEGD (i blandinger), COMGHA, DINA, ATBC og GTA. De fleste af disse har deres egne

miljøproblemer, men mange af dem anses ov erordnet set som havende bedre miljøegenskaber end

DEHP baseret på den tilgængelige information. En direkte sammenligning mellem DINP, DIDP og

DPHP med deres alternativer er ikke fundet.

En bred søgning af alternativer til ftalaterne DEP, DIPP og DMEP har ikke været mulig i dette

projekt. Hvad angår DEPs anvendelse som denatureringsmiddel findes der dog mange alternativer

og DEP er ikke på 2013 listen over denatureringsmidler, der kan give afgiftsfritagelse for national

alkoholafgift i EU lande, herunder Danmark. Vurderet ud fra en review fra 2010 af alternativer til

DEHP, DBP og BBP er der klare indikationer af at der er ikke-ortho-ftalat alternativer til rådighed,

der dækker hovedanvendelserne af DEP, DIPP og DMEP. Eksempler er GTA, ATBC, COMGHA,

DINCH, DINA, DGD, ASE og en blanding med DEGD som hovedkomponent.

Hv ad angår alternative materialer med egenskaber som ligner blød PVCs er de følgende bløde

poly merer blandt hovedalternativerne: Ethylene vinyl acetate (EVA), Low density polyethylene

(LDPE), poly olefin elastomerer, polyurethaner (kan i visse tilfælde være blødgjort med ftalater),

isobutyl gummi, EPDM (kan i v isse tilfælde være blødgjort med ftalater) og silikone gummi.


Manglende oplysninger

Sammenfattende må anvendelsen af de generelle blødgørere DINP og DIDP anses som

v elbeskrevet, selvom en reel fordeling af deres anvendelse på slutprodukter ikke findes for

Danmark. DPHP er mindre velbeskrevet, men har funktionelle egenskaber svarende til DIDP og

kan anvendes som alternativ til denne. Hvad angår DEP, så antyder den registrerede mængde, samt

andre oplysninger, at den stadig har en betydelig anvendelse i EU, men flere detaljer om dens

anvendelse er nødvendige. DIPP ser ud til at have en meget afgrænset anvendelse i EU og det er

spørgsmålet om der kan findes mere relevant information om den. DMEP er forstsat ikke

registreret og det kan antyde at dens fremtidige anvendelse i EU er meget begrænset eller helt

fraværende.

De følgende større databehov er således identificeret:

Mere specifik information om brugen af DINP, DIDP, DPHP og DEP med særlig fokus på

DINP og DEP på grund af stoffernes toksikologiske egenskaber..

Undersøgelse af blød PVCs skæbne i affaldshåndteringen i Danmark, herunder

indsamlingsrater, for både husholdningsaffald og erhvervsaffald.

Information om direkte alternativer til DEP i v æsentlige anvendelsesområder på baggrund af

produktionsmængder og deraf følgende mulig eksponering..

Direkte sammenligninger mellem DINP, DIDP og DPHP og deres (respektive) tilgængelige

alternativer for relevante anvendelser.

Identifikation af de v igtigste metabolitter, som kan anvendes som en biomarkører for humane

eksponeringer

Begrænset information om hormonforstyrrende virkning for nogle ftalater

Yderligere dokumentation for virkningerne af kumulativ eksponering for fx anti-androgene og

østrogene stoffer på forskellige niveauer


25

1. Introduction to the substance group

1.1 Definition of the substances

The term "phthalate" is generally used to identify diesters of orthophthalic acid which is an

aromatic dicarboxylic acid in which the two carboxylic acid groups are located in the ortho position

in the benzene ring. The general chemical structure is shown below where the ester side chains (R),

commonly ranging from C4 to C13, may be linear, branched or a combination of linear, branched,

and ringed.

O

O

O

O

R

R

Generally both side chains are structurally identical as it is the case for the phthalates included in

the present survey, but they may differ in other phthalates. The specific characteristics affect the

phy sicochemical and toxicological properties of the phthalate.

Phthalates are divided into low -molecular phthalates and high-molecular phthalates based on the

number of carbon atoms in the chains. Low Molecular Weight (LMW) phthalates, include those

with 3-6 carbon atoms in their chemical backbone and 3-8 total carbons in the alkyl side chains.

High Molecular Weight (HMW) phthalates, include those with 7 -13 carbon atoms in their chemical

backbone and 3-8 total carbons in the alkyl side chains (ECPI, 2013f).

The group of selected phthalates includes the substances shown in Table 1. The status of the

substances as low or high molecular weight substances is also indicated.


TABLE 1

OVERVIEW OF SUBSTANCES COVERED BY THE SU RVEY

A bbre-

v iation

Su bstance na m e EC No CA S No St ru ct u re *1

DEP Diethyl phthalate 2 01-550-6 8 4-66-2

LMW

DIPP Diisopentyl

ph thalate

2 10-088-4 6 05-50-5

LMW

DPHP Bis(2-propylheptyl)

ph thalate

2 58-469-4 5 3306-54-0

HMW

DMEP Bis(2-methoxyethyl)

ph thalate

2 04-212-6 117-82-8

LMW

DINP

*2

1 ,2-

Ben zenedicarboxylic

a cid, di-C8-10-

br anched alkyl

esters, C9-rich

Di-''ison onyl''

ph thalate

27 1-090-9

2 49-079-5

6 8515-48-0

2 8553-12-0

HMW


27

A bbre-

v iation

Su bstance na m e EC No CA S No St ru ct u re *1

DIDP

*2

1 ,2-


a cid, di-C9-11-

br anched alkyl

esters, C10-rich

Di-''isodecyl''

ph thalate

27 1-091-4

2 47-977-1

6 8515-49-1

2 6761-40-0

HMW

*1 Source: ECHA registrations (DEP, DIPP, DPHP, DMEP); EU RAR: DINP, DIDP. Note that the structures

sh own for DINP and DIDP are examples, as each of these “substances” actually is a mix of substances with

a n average stoichiometric composition of di-nonyl phthalate and di-decyl phthalate, respectively.

*2 For DINP and DIDP two CAS numbers are listed because the substance composition varies slightly with the

pr oduction process used and because both numbers are addressed in much of the available literature.

DINP and DIDP constitute mixtures of substances which are further described in ECHAs

Ev aluation of New Scientific Ev idence Concerning DINP and DIDP in Relation to Entry 52 of Annex

XVII to Regulation (EC) No 1907/2006 (REACH) (ECHA, 2013) and cited under the substance

headings below.

DINP

Two different types of DINP are currently on the market:

DINP-1 (CAS No 68515-48-0) is manufactured by the “Polygas” process.

DINP-2 (CAS No 28553-12-0) is n-butene based. (EC 2003a)

The production of a third form DINP-3 (also CAS 28553-12-0) has reportedly been discontinued

(EC 2003a).

According to the trade organisation European Council of Plasticisers and Intermediates, ECPI

(ECPI, 2011d), DINP is composed of different alcohol chains depending on the production method.

It is a manufactured substance made by esterifying phthalic anhydride and isononanol. Isononanol

is composed of different branched C9 alcohol isomers. The two branches on the molecule R1 and R2

are not necessary identical, and are either mainly C8H17 to C1 0H21 (DINP-1) or C9H19 isomers (DINP-

2).

DINP-1 (CAS No 68515-48-0) contains alcohol groups made from octane, by the “polygas” process

(EC 2003a). At least 95 percent of these alcohol groups comprise roughly equal amounts of 3 ,4-,

3 ,5-, 3,6-, 4,5-, 4,6-, and 5,6-dimethyl heptan-1-ol (Hellwig et al. 1 997 as cited in Babich and

Osterhout 2010). DINP-1 is also known by the trade name JayflexR.

DINP-2 (CAS No 28553-12-0) contains alcohol groups made from n-butene, which results mainly in

methyl octanols and dimethyl heptanols. DINP-2 is also known by the trade names Palatinol NR

and Palatinol DNR (NLM 2009a). DINP-3 (also CAS No 28553-12-0) contains alcohol groups made

from n-butene and i-butene, resulting in 60 percent methylethyl hexanols. DINPs generally contain

7 0% or more nonyl alcohol moieties, with the remainder being octyl or decyl (Madison et al. 2000

as cited in Babich and Osterhout 2010).


Although their isomeric composition differs, the different types of DINP are considered to be

commercially interchangeable. (Babich and Osterhout 2010).

The percent composition of the different chain structures of the two forms of DINP is shown in

Table 10.

TABLE 2

BEST ESTIMATE OF CON TEN T (%) OF THE DIFFEREN T CHAIN STRUCTURES OF THE DINP ’S (EC, 2003A)

Su bstance name DINP-1 DINP-2

Met hylethyl hexanols 5 -10 5 -10

Dim ethyl heptanols 4 5-55 4 0-45

Met hyl octanols 5 -20 3 5-40

n -Nonanol 0-1 0-10

Isodecanol 15-25 --

DIDP

Two different types of DIDP are currently on the market:

DIDP-1 (CAS No 26761-40-0)

DIDP-2 (CAS No 68515-48-0)

DIDP is a complex mixture containing mainly C10-branched isomers (EC 2003b). DIDP is

marketed under two CAS numbers. No data on the differences between the types of DIDP has been

identified and the EU Risk Assessment (EC 2003b) does not distinguish between the different

forms (unlike the Risk Assessm ent for DINP).

The correct structures can only be estimated. Based on nonene (CAS No 97593-01-6) isomer

distribution analysis and 1H-NMR analysis of isodecyl alcohol, the EU Risk Assessment provides an

estimation of key isomeric structures of isodecy lalcohol and hence of DIDP, as shown in Table 2.

The lower ranges do not add up to 1 00% indicating that the substance may include other chain

lengths.

TABLE 3

BEST ESTIMATE OF CON TEN T (%) OF THE DIFFEREN T CHAIN STRUCTURES OF THE DIDP (EC, 2003B)

Lon gest chain (estimate) DIDP (CA S 68515-49-1 & CA S 26761-40-0)

Best estimat ed con t ent (%)

C7 tr i-m eth y l h epta n ols 0-10

C8 di-m eth y l octa n ols 7 0-80

C9 m eth y l n on a n ols 0-10

C10 n -deca n ol

1.2 Phy sical and chemical properties

The physico-chemical properties of the selected phthalates presented in the tables below are where

av ailable referred from the REACH registration dossiers on the home page of the European

Chemicals Agency (ECHA).


29

TABLE 4

N AME AN D OTHER IDENTIFIERS OF DIETHYLPHTHALATE (DEP)

Diet h y l ph t h a la t e (DEP) Reference

Sy nonyms Diethyl benzene-1,2-dicarboxylate, 1,2-

Ben zenedicarboxylic acid, diethyl ester

Molecular formula C 12H 14O4

Reg istration at ECHAs website

Molecular weight

range

2 22.24 Na tional Toxicology Programme

Ph ysical state Liqu id (25 °C) Reg istration at ECHAs website

Melting/freezing point -6 0 °C Reg istration at ECHAs website

Boiling point 2 97.3 °C (101.3 kPa) Reg istration at ECHAs website

Relative density 1118.1 kg/m 3 (20 °C) Reg istration at ECHAs website

V apour pressure < 2 8 mBar (25 °C) Reg istration at ECHAs website

Su rface tension 37 .5 dynes/cm (20 °C)

Na tional Toxicology Programme

Wa ter solubility

(m g/L)

9 32 mg/L (20 °C) Reg istration at ECHAs website

Log P (octanol/water) 2 .47 Na tional Toxicology Programme

TABLE 5

N AME AN D OTHER IDENTIFIERS OF DIISOPENTYL PHTHALATE (DIPP)

Diisopent y l ph t h a la t e (DIPP) Reference

Sy nonyms Bis(3-methylbutyl) phthalate; diisoamyl

ph thalate


Molecular formula C 18H26O4 Reg istration at ECHAs website

Molecular weight

range

3 06.41

Ph ysical state Liqu id (20 °C, 1013 hPa) Reg istration at ECHAs website

Melting/freezing point < -2 5 °C Reg istration at ECHAs website

Boiling point 3 39 °C (1016 mBar) Reg istration at ECHAs website

Relative density 1 .02 (20 °C) Reg istration at ECHAs website

V apour pressure 0.025 Pa (25 °C) Reg istration at ECHAs website


Diisopent y l ph t h a la t e (DIPP) Reference

Su rface tension 5 8 mN/m (20 °C) Reg istration at ECHAs website

Wa ter solubility

(m g/L)

1 .1 mg/L (20 °C) Reg istration at ECHAs website

Log P (octanol/water) 5 .45 (KowWin) Reg istration at ECHAs website

TABLE 6

N AME AN D OTHER IDENTIFIERS OF BIS(2-PROPYLHEPTYL) PHTHALATE (DPHP)

Bis(2-propy lh ept y l) ph t h a la t e

(DPHP)

Reference

Sy nonyms 1 ,2-benzenedicarboxylic acid, di-2-

pr opylheptyl ester


Molecular formula C28H46O4 Reg istration at ECHAs website

Molecular weight

range

4 46,7 Reg istration at ECHAs website


Melting/freezing point - 4 8 °C (pour point) Reg istration at ECHAs website

Boiling point 2 52.5 – 253.4 °C (7 hPa) Reg istration at ECHAs website

Relative density 0.96 (20 °C) NICNAS, 2003

V apour pressure 0.000000037 hPa (20 °C) Reg istration at ECHAs website

Su rface tension 3 5.1 dyne/m (20 °C) h ttp://www.lookchem.com/Bis-2-

pr opylheptyl-phthalate/

Wa ter solubility

(m g/L)

< 0,0001 mg/L (25 °C) Reg istration at ECHAs website

Log P (octanol/water) 1 : > 6 (25 °C; pH 5,77)

2 : 10.36 (25 °C) (QSAR)


*) http://www.cpsc.gov//PageFiles/125788/dphp.

http://www.lookchem.com/Bis-2-propylheptyl-phthalate/

http://www.lookchem.com/Bis-2-propylheptyl-phthalate/

http://www.cpsc.gov/PageFiles/125788/dphp.


31

TABLE 7

N AME AN D OTHER IDENTIFIERS OF BIS(2-METHOXYETHYL) PHTHALATE (DMEP)

Bis(2-m et h oxy et h y l) ph t h a la t e

(DMEP)

Reference

Sy nonyms 1 ,2-Benzenedicarboxylic acid, bis(2-

m ethoxyethyl) ester

NICNAS, 2008

Molecular formula C 14H 18O6

Molecular weight

range

2 82.3 NICNAS, 2008

Ph ysical state Liqu id NICNAS, 2008

Melting/freezing point - 4 0 °C NICNAS, 2008

Boiling point 3 40 °C NICNAS, 2008

(Relative) density 1 .170 g/cm3 NICNAS, 2008

V apour pressure < 0.013 kPa (20 °C) NICNAS, 2008

Su rface tension 4 0.5 dyne/m h ttp://www.chemspider.com/Chem

ical-Structure.8041.html

Wa ter solubility

(m g/L)

0.9 g/L (20 °C) NICNAS, 2008

Log P (octanol/water) 2 .9 NICNAS, 2008

TABLE 8

N AME AN D OTHER IDENTIFIERS OF 1,2-BEN ZENEDICARBOXYLIC ACID, DI-C8-1 0-BRANCHED ALKYL ESTERS, C9-

RICH (DIN P)

1,2-Benzenedicarboxylic acid, di-C8-

10-branched a lky l est ers, C9-rich

(DINP)

Reference

Sy nonyms Di-iso-nonyl phthalate; 1,2-

benzenedicarboxylic acid, di-isononyl ester

Molecular formula C26H42O4

Molecular weight

range

4 20.6 ECB, 2003a


Melting/freezing point < -5 0 °C (pour point: - 54 °C) Reg istration at ECHAs website

Boiling point > 4 00 °C (1 atm) (calc)

3 31 °C (96.47 kPa) (exp)


http://www.chemspider.com/Chemical-Structure.8041.html

http://www.chemspider.com/Chemical-Structure.8041.html


(Relative) density 0.97 g/cm3 (20 °C) Reg istration at ECHAs website


Su rface tension 3 0.7 mN/m (20 °C) Reg istration at ECHAs website

Wa ter solubility

(m g/L)

0.6 µg /L (21 °C, pH 7) Reg istration at ECHAs website

Log P (octanol/water) 8 .8 (25 °C, pH 7) Reg istration at ECHAs website

TABLE 9

N AME AN D OTHER IDENTIFIERS OF 1,2-BEN ZENEDICARBOXYLIC ACID, DI-C9-1 1-BRANCHED ALKYL ESTERS, C1 0-

RICH (DIDP)

1,2-Benzenedicarboxylic acid, di-C9-

11-branched alkyl est ers, C10-rich

(DIDP)

Reference

Sy nonyms Di-isodecyl phthalate; 1,2-

benzenedicarboxylic acid, di-isodecyl ester

Molecular formula C28H46O4

Molecular weight

range

4 47 Reg istration at ECHAs website


Melting/freezing point - 45 °C (101325 Pa) Reg istration at ECHAs website

Boiling point 4 63 °C (1013 hPa) Reg istration at ECHAs website

(Relative) density 0.97 g/cm3 (20 °C) Reg istration at ECHAs website


Su rface tension 3 0.9 mN/m (20 °C) Reg istration at ECHAs website

Wa ter solubility

(m g/L)

0.0381 µg/L (25 °C, pH 7) Reg istration at ECHAs website

Log P (octanol/water) 9 .46 (25 °C, pH 7) Reg istration at ECHAs website

* h ttp://echa.europa.eu/web/guest/information-on-chemicals/registered-substances.

1.3 Function of the substances for the m ain application areas

Phthalates are primarily used to soften and make PVC flexible. They are however also found in

other product types where they e.g. are added to avoid stiffness and cracking of surface films or

because of their adhesive properties.

Phthalates belong to the group of general purpose (GP) plasticisers which provide the desired

flexibility to PVC along with an overall balance of optimum properties at the lowest cost (Wilkes et

al., 2005). Phthalates are external plasticisers which mean that they are not firmly chemically

bound to the plastic but are only dispersed in it. As a result, these plastici sers may degas or migrate

http://echa.europa.eu/web/guest/information-on-chemicals/registered-substances


33

from the plastic under certain conditions, and they can be released in relatively large proportions,

e.g. when in contact with lipophilic media (such as oil or grease).

An effective plasticiser in PVC, must contain two types of structural components, polar and apolar.

The polar portion of the molecule must be able to bind reversibly with the PVC polymer, thus

softening the PVC, while the non-polar portion of the molecule allows the PVC interaction to be

controlled so it is not so powerful a solvent as to destroy the PVC crystallinity. Examples of polar

components would be the carbonyl group of carboxylic ester functionality; the non -polar portion

could be the aliphatic side chain of an ester. The balance between the polar and non -polar portions

of the molecule is critical to control its solubilising effect. If a plasticizer is too polar, it can destroy

PVC crystallites; if it is too non-polar, compatibility problems can arise (Wilkes et al., 2005).

Sev eral theories are developed to account for the observed characteristics of the plasticisation

process, e.g. the theory of free volume. Free volume is a measure of the internal space available

within a polymer. As free volume is increased, more space or free volume is provided for molecular

or poly mer chain movement. A polymer in the glassy state has its molecules packed closely but is

not perfectly packed. The free volume is low and the molecules cannot move past each other very

easily. This makes the polymer rigid and hard. When the polymer is heated to above the glass

transition temperature, Tg, the thermal energy and molecular vibrations create additional free

v olume which allows the polymer molecules to move past each other rapidly. This has the effect of

making the polymer system more flexible and rubbery. Free volume can be increased through

modifying the polymer backbone, such as by adding more side chains or end groups. When small

molecules such as plasticisers are added, this also lowers the Tg by separating the PVC molecules,

adding free volume and making the PVC soft and rubbery. Molecules of PVC can then rapidly move

past each other.

Glass transition temperature is the temperature at which a polymer changes from a glassy brittle

state to a fluid flexible state. PVC has a glass transition temperature of about 80 degrees centigrade ,

well above room temperature and it is therefore brittle at room temperature. Low density

poly ethylene (LDPE) on the other hand has a glass transition temperature below 0 degrees.

Therefore it is flexible and not brittle at normal room temperatures, and w ould not be expected to

require a plasticizer to keep it flexible (http://www.consultingchemist.com/Phthalates.pdf)

DINP

DINP is a general plasticiser, which is applied in many products as th e direct alternative for DEHP,

the formerly major general PVC plasticiser in the EU. As such DINP has a high consumption and is

probably the plasticiser which can be found in most flexible PVC products produced in the EU

today.

DIDP

DIDP has slightly higher weight and lower solubility than DINP and is thus mainly used in

applications where continued product quality is needed under more demanding conditions, such as

elev ated temperatures, for example in electric cables. A major DIDP use is consequently as

plasticiser in PVC insulation on cable and wiring. Other uses include car interiors and PVC flooring.

DPHP

According to ECPI’s DPHP site (2013), a lmost all DPHP is used as a plasticiser to make PVC soft

and flexible. Owing to its low volatility and weathering resistance, DPHP is suitable for high

temperature applications such as wire and cable and automotive interior trim and outdoor

applications such as roofing membranes and tarpaulins.

http://www.consultingchemist.com/Phthalates.pdf


DEP

DEP is a specialty polymer plasticiser and a solvent for cosmetics and personal care products,

among others. It is a low-weight phthalate; these generally have higher volatility and mobility in the

poly mer when used as plasticisers. Plasticiser uses include cellulose polymers, nail polishes, etc. An

example of a solv ent application is as a bearer of fragrances, and a delayer of release of the

fragrance, in cosmetics and personal care products. It has also been used as a denaturant in alcohol

for cosmetics and personal care products (and possibly in other applications).

DIPP

DIPP has been registered for its use in the manufacture of propellants (explosives in ammunition).

As other low molecular weight phthalates DIPP may also be used as plasticiser for PVC products

and other polymers. However there is currently no regist ration for that use. According to ECPI

(2013e), DIPP is not produced in Europe anymore.

DMEP

DMEP is a specialty plasticiser which can be used in a number of polymers. According to BAuA

(2011), only limited information regarding DMEP in consumer products in the European

marketplace has been identified. The Australian NICNAS (2008) has reported about the import of

DMEP in balls for playing and exercise, hoppers and children’s toys (e.g. as inflatable water

products). CPSC (2011) reports its use as a plasticiser (in the USA), but it is not mentioned if these

are current observations.

According to ECPI (2013e), DMEP is not used as a plasticiser and the only European producer

stopped making this substance a few years ago. As of June 2013, DMEP has not been registered

under REACH.


35

2. Regulatory framework

This chapter gives an overview of how the selected phthalates are addressed in existing and

upcoming EU and Danish legislation, international agreements and also by eco-label criteria.

In Appendix 1: a brief ov erview of legal instruments in the EU and DK and how they are related is

presented. The appendix also gives a brief introduction to the chemicals legislation, it explains the

lists referred to in section 2.1.3, and it provides a brief introduction to international agreements and

selected eco-label schemes.

2.1 Legislation

This section will first list existing legislation addressing the selected phthalates and then give an

ov erview of on-going activities, focusing on which substances are in the pipeline in relation to

v arious REACH provisions.

2.1.1 Existing legislation

Table 10 provides an ov erview of existing legislation addressing the selected phthalates. For each

area of legislation, the table first lists the EU legislation (if applicable) and then the transposition of

this into Danish law and/or other national rules where this is required. National rules will only be

elaborated upon in case the Danish rules differ from EU rules. For each legislative area the name of

the Competent authority is mentioned in the heading.

In addition to the legislation concerning named substances the phthalates will of course also be

cov ered by criteria-based legislation where relevant, e.g. bans and restrictions covering substances

classified as toxic for reproduction which would concern DIPP and DMEP. This includes as an

example the new rules for toys which prohibit CMR-classified substances in concentrations above

the specific classification limit in all accessible components of toy s.


TABLE 10

EU AN D DAN ISH LEGISLATION ADDRESSIN G SELECTED PHTHALATES (AS OF JU LY 2013)

Legal instrument *1 EU/DK Su bst a nces Requ irem ent s

Legislation addressing products (Danish EPA)

Regulation No 1907/2006

con cerning the

Registration, Evaluation,

A uthorisation and

Restriction of Chemicals

(REA CH)

EU In cluded in Annex

XV II, no. 52:

(a ) Di-‘isononyl’

ph thalate (DINP)

CA S No 28553-12-0

a n d 68515-48-0; EC

No 2 49-079-5 and

27 1-090-9

(b) Di-‘isodecyl’

ph thalate (DIDP)

CA S No 26761-40-0

a n d 68515-49-1 EC

No 2 47-977-1 and

27 1-091-4

Th e listed phthalates::

(1 ) Shall not be used as substances or in mixtures, in

con centrations greater than 0.1 % by weight of the

pla sticised material, in toys and childcare articles

w hich can be placed in the mouth by children.

(2 ) Such toys and childcare articles containing these

ph thalates in a concentration greater than 0.1 % by

w eight of the plasticised material shall not be placed

on the market.

(3 ) The Commission shall re-evaluate, by 16 January

2 010, the measures provided for in relation to this

en try in the light of new scientific information on

su ch substances and their substitutes, and if

ju stified, these measures shall be modified

a ccordingly.

(4 ) For the purpose of this entry ‘childcare article’

sh all mean any product intended to facilitate sleep,

r elaxation, hygiene, the feeding of children or

su cking on the part of children.

St atutory Order on the ban

on phthalates in toys and

ch ildcare articles

(Bekendtgørelse om forbud

m od ftalater i legetøj og

sm åbørnsartikler til børn i

a lderen 0-3 år, BEK Nr. 855

a f 5 September 2009)

DK A ll phthalates

ex cept DEHP, DBP,

BBP, DINP, DIDP

a n d DNOP

(Cov ered by

Regulation No.

1 907/2006/EC)

Ba n on the import, sale and use of phthalates in toys

a n d childcare articles for children aged 0-3 years if

th e products contain more than 0.05 per cent by

w eight of phthalates.

DIRECT IVE 2009/48/EC of

18 Ju ne 2009 on the safety

of t oys

St atutory Order on the

sa fety of toys

(Bekendtgørelse om

sikkerhedskrav til

legetøjsprodukter, BEK nr

13 a f 10/01/2011)

EU

DK

CMR su bstances

(including DMEP

a n d DIPP)

CMR su bstances are as of 20 July 2013 banned in all

a ccessible components of toys in concentrations

a bove the specific classification limit.

https://www.retsinformation.dk/Forms/R0710.aspx?id=126137




37


Legislation addressing cosmetics (Danish EPA)

REGULATION (EC) No

1223/2009 of 30 November

2009 on cosmetic products

EU bis(2-Methoxyethyl)

ph thalate (DMEP)

(CAS no. 117-82-8)

a n d

Diisopentylphthalate

(DIPP) (CAS no.

6 05-50-5)

In cluded in Annex II (LIST OF SUBSTANCES

PROHIBITED IN COSMETIC PRODUCTS)

Legislation addressing medical devices (Ministry of Health and Prevention)

DIRECT IVE 2007/47/EC

of 5 September 2007

amending Council Directive

90/385/EEC on the

a pproximation of the laws

of t he Member States

relating to active

im plantable medical

devices, Council Directive

93/42/EEC con cerning

m edical devices and

Directive 98/8/EC

con cerning the placing of

biocidal products on the

m arket.

St atutory Order concerning

m edical devices

(Bekendtgørelse om

m edicinsk udstyr nr.1263

a f 15/12/2008)

EU

DK

Ph thalates classified

a s r eproductive

toxicants in category

1 or 2 (DIPP and

DMEP)

La belling requirement for certain medical devices

con taining the phthalates and requirements for

in formation about risks.

Legislation addressing emissions (Danish EPA)

St atutory Order on water

qu ality and monitoring of

wa ter supply system

(Bekendtgørelse om

v andkvalitet og tilsyn med

v andforsyningsanlæg, BEK

nr 1024 af 31/10/2011)

DK Ph thalates other

than DEHP

(DEHP is

specifically

m entioned)

Th e sum of phthalates other than DEHP must not

ex ceed 1 µg/L in water leaving the waterworks and at

th e point of entering consumer properties. The value

a t the consumers tap must not exceed 5 µg/L water.

(A ll values are 1 µg/L for DEPH)



St atutory Order on quality

requirement to

environmental analyses

(Bekendtgørelse om

kvalitetskrav til

m iljømålinger, BEK no 900

a f 17/08/2011

DK Pla sticisers

in cluding the sum of

diisononylphthalates

(DINP)

Sets requirements concerning quality control of

ch emical analyses of environmental and product

samples and requirements concerning standard

dev iation on the measurements. Concerns analyses

pr epared as part of the authorities’ enforcement of

th e Danish Environmental Protection Act, the

Ch emical Substances and Products Act and other

legal instruments in the field of the environment and

a nalysis prepared as part of environmental

m onitoring programmes.

Legislation addressing occupational health and safety (Ministry of Employment)

St atutory Order on

occu pational limit values

for substances and

m aterials (Bekendtgørelse

om grænseværdier for

st offer og materialer, BEK

nr 507 af 17/05/2011 – with

later amendments)

DK Diethyl phthalate

(DEP) (CAS no. 84-

6 6-2)

A limit value of 3 mg/m 3 is established for DEP

(g asses, vapours and particulates) in workplace air.

Cou ncil Directive 98/24/EC

of 7 A pril 1998 on

protection of

t he health and safety of

workers from the risks

related to

ch emical agents at work.

St atutory order nr. 292 of

26 A pril 2001 on working

with

su bstances and materials

(ch emical agents) – with

later

a mendments.

EU

DK

Classified phthalates


39


Legislation addressing food contact materials (Ministry of Food, Agriculture and Fisheries)

REGULATION (EU) No

10/2011 of 14 January 2011

on plastic materials and

a rticles intended to come

into contact with food

EU In cluded in Annex I,

FCM subst. no. 728

a n d 729:

(a ) Di-‘isononyl’

ph thalate (DINP)

CA S No 28553-12-0

a n d 68515-48-0; EC

No 2 49-079-5 and

27 1-090-9

(b) Di-‘isodecyl’

ph thalate (DIDP)

CA S No 26761-40-0

a n d 68515-49-1 EC

No 2 47-977-1 and

27 1-091-4

Ma nufacture and marketing of plastic materials and

a rticles:

DINP a nd DIDP in plastic materials and articles:

(a ) intended to come into contact with food; or

(b) already in contact with food; or

(c) which can reasonably be expected to come into

con tact with food;

m ust only be used as:

(a ) plasticiser in repeated use materials and articles;

(b) plasticiser in single-use materials and articles

con tacting non-fatty foods except for infant formulae

a n d follow-on formulae as defined by Directive

2 006/141/EC or processed cereal-based foods and

ba by foods for infants and young children as defined

by Directive 2006/125/EC;

(c) technical support agent in concentrations up to

0,1 % in the final product.

Legislation addressing tariffs (Ministry of Taxation)

La w on the taxation of

polyvinylchloride and

ph thalates (Danish PVC

T a x Act)

(Bekendtgørelse af

lov om afgift a f

polyvinylklorid og ftalater

(PV C-afgiftsloven), LBK nr

253 a f 19/03/2007)

DK Flexible (and hard)

PV C with content of

ortho-phthalate

esters

Goods made of PVC or PVC with phthalates for the

m ost important applications are subject to tax based

on the type and weight of the PVC goods marketed in

Denmark. Rates are set for each article/material

ca tegory; flexible PVC documented to be without

ph thalate contents have substantially lower tax rates.

Th e Act covers a large number of g oods categories

con taining PVC or PVC and phthalates.

Legislation addressing waste

Directive 2008/98/EC of 19

Nov ember 2008

on waste and repealing

certain Directives – The

Wa ste Directive

EU (In this context:)

Classified

su bstances, that is

DIPP a nd DMEP

Sets out criteria for waste definitions and handling,

in cluding defining waste as hazardous waste if it

ex hibits specified toxic properties.

St atutory Order on waste

(A ffaldsbekendtgørelsen) -

BEK 1309 a f 18. dec. 2012

DK = Im plements the Waste Directive in DK. Specifies

threshold concentrations for waste including

su bstances with specified classifications, including

Repr. 1 substances (DIPP and DMEP), for which the

con centration threshold is 0.5%. Waste above this

limit is to be considered hazardous waste and be

tr eated as such.



Directive 94/62/EC of 20

December 1994

on packaging and

pa ckaging waste (as later

a mended) – the Packaging

Directive

EU Ha zardous

su bstances in

g eneral

Does n ot explicitly mention phthalates, but states

that “Packaging shall be so manufactured that the

pr esence of noxious and other hazardous substances

a n d materials as constituents of the packaging

m aterial or of any of the packaging components is

m inimized with regard to their presence in

em issions, ash or leachate when packaging or

r esidues from management operations or packaging

w aste are incinerated or landfilled.”

St atutory Order on

pa ckaging

(Em ballagebekendtgørel-

sen; BEK 1049 af

10/11/2011)

DK = Im plements the Packaging Directive in DK.

St atutory Order on sewage

sludge

(Slambekendtgørelsen -

BEK nr. 1650 af 13. dec.

2006).

DK Does n ot specifically mention the substances

in cluded in this review, but sets a threshold value for

th e concentration of the phthalate DEHP in sewage

slu dge used for agricultural purposes: 50 mg/kg dry

m atter.

Regulation EC 1013/2006

of 14 June 2006

on shipments of waste

EU Wa ste Does n ot specifically mention the substances

in cluded in this review. Regulates trans-boundary

transport of waste (implements the Basel Convention

in the EU).

*1 Un -official translation of name of Danish legal instruments.

As illustrated by the table, Denmark has national rules banning the use of phthalates in toys and

childcare articles intended for children under 3 years. These rules exclude DINP and DIDP, which

however are covered by the EU ban for toys and childcare articles intended to be placed in the

mouth.

2.1.2 Classification and labelling

Harmonised classification in the EU

Table 11 lists the two phthalates (DIPP and DMEP) for which a harmonised CLP classification has

been agreed upon. It shows that both substances are classified for reproductive toxicity in category

1 B and that DIPP is classified as acute toxic 1 in aquatic environments.

Industry classifications for substances without a harmonised classification and labelling agreement

are summarised in Table 12 and will be taken into account in Chapters 5 and 6 on environment and

human health assessments.


41

TABLE 11

HARMON ISED CLASSIFICATION ACCORDING TO ANNEX VI OF REGULATION (EC) N O 1 272/2008 (CLP REGU LA TION )

Index No International

Ch emical

Identification

CA S No Cla ssification

Ha zard Class and

Ca tegory Code(s)

Ha zard

st atement

Code(s)

607-426-00-1 Diisopentylphthalate

(DIPP)

6 05-50-5 Repr. 1B

A quatic Acute 1

H360FD

H400

607-228-00-5 Bis(2-methoxyethyl)

ph thalate (DMEP)

117-82-8 Repr. 1B H360Df

Self-classification in the EU

The Classification & Labelling (C&L) Inventory database at the website of the European Chemicals

Agency (ECHA) contains classification and labelling information on notified and registered

substances submitted by manufacturers and importers. The database includes as well the

harmonised classification. Companies have provided this information in their C&L notifications or

registration dossiers (ECHA, 2013d). ECHA maintains the Inventory, but does not v erify the

accuracy of the information.

Classifications of DEP, DPHP, DINP and DIDP listed in the database are shown in the table below.

Substances with a harmonised classification are not indicated, reference is made to the table above.

In the table the total number of notifiers is indicated first followed by the number of notifiers that

have classified the substance in each individual hazard class, e.g. Acute tox 1. The full classification

submitted by the notifiers can be seen in the overview on ECHAs homepage.

TABLE 12

CLASSIFICATION INFORMATION OM N OTIFIED AND REGISTERED SU BSTANCES RECEIVED FROM MAN UFACTURERS

AN D IMPORTERS (C&L IN VEN TORY)

CA S No

Su bst a nce na m e Ha zard Class and

Ca tegory Code(s)

Ha za rd

St a t em ent

Codes

Nu m ber of

not ifiers

84-66-2 Diethyl phthalate (DEP) T otal

A cute Tox. 1

A cute Tox. 1

Skin Irrit. 2

Skin Sens. 1

Ey e Irrit. 2

A cute Tox. 3

A cute Tox. 4

STOT SE 3

Repr. 2

STOT RE 2

H302

H312

H315

H317

H319

H331

H332

H335

H361

H373

70

1

1

11

1

15

1 6

4

9

2

1 0

53306-54-0 Bis(2-propylheptyl)

ph thalate (DPHP)

T otal

Not classified

126

1 26


CA S No

Su bst a nce na m e Ha zard Class and

Ca tegory Code(s)

Ha za rd

St a t em ent

Codes

Nu m ber of

not ifiers

68515-48-0

1 ,2-Benzenedicarboxylic

a cid, di-C8-10-branched

a lkyl esters, C9-rich

(DINP)

T otal

Not classified

Skin Irrit. 2

Ey e Irrit. 2

Repr. 2

A quatic Acute 1

H315

H319

H361

H400

269

2 40

1

1

3

2 4

28553-12-0 Di-''ison onyl'' phthalate

(DINP)

T otal

Not classified

A cute Tox. 4

A quatic Acute 1

A quatic Chronic 1

A quatic Chronic 4

H332

H400

H410

H413

857

7 81

1

2 4

2 3

2 8

68515-49-1

1 ,2-Benzenedicarboxylic



(DIDP)

T otal

Not classified

Skin Irrit. 2

Ey e Irrit. 2

H315

H319

410

3 53

2 5

3 2

26761-40-0 Di-''isodecyl'' phthalate

(DIDP)

T otal

Not classified

Skin Irrit. 2

Ey e Irrit. 2

A quatic Acute 1

A quatic Chronic 1

A quatic Chronic 2

H315

H319

H400

H410

H413

182

97

1

1

4 1

2 3

4 3

2.1.3 REACH

Candidate list

As of August 2013, two of the selected phthalates have been included in the candidate list as

substances meeting the criteria for classification in the hazard class reproductive toxicity category

1 B.

TABLE 13

SELECTED PHTHALATES ON THE CANDIDATE LIST (ECHA, 201 3B; LAST U PDATED: 20/06/201 3)

CA S No EC No Su bst a nce Na m e Da t e of

inclu sion

Rea son for inclusion Decision nu m ber

605-50-5 210-088-4 Diisopentyl phthalate

(DIPP)

2 012/12/19 Tox ic for reproduction

(A rticle 57 c)

ED/1 69/2012

117-82-8 204-212-6 Bis(2-methoxyethyl)

ph thalate (DMEP)

2 011/12/19 Tox ic for reproduction

(A rticle 57 c)

ED/7 7 /2011

Authorisation List / REACH Annex XIV

As of March 2013, none of the selected phthalates are included in REACH annex XIV which is a list

of substances that require authorisation for continued use in the EU.


43

Community rolling action plan

Table 14 shows the grounds for concern in relation to the planned REACH substance evaluation of

DEP that may lead to further community action in the form of e.g. a restriction or authorisation.

TABLE 14

SU BSTAN CES IN THE DRAFT COMMU N ITY ROLLIN G ACTION PLAN, 201 3-2015 U PDATE (ECHA, 201 2A)

CA S No EC No Su bst a nce

Na m e

Yea r Mem ber St a t e Initial grounds for concern

84-66-2 2 01-550-6 Diethyl phthalate 2 014 Germany/Portugal* Su spected Endocrine Disruptor;

Ex posure/Wide dispersive use,

con sumer use, high aggregated

tonnage

* Where two Members States are indicated, this is a joint evaluation. The first Member State mentioned

lea ds the Ev aluation and is the responsible competent authority in the meaning of Article 45(2) of REACH.

Registry of Intentions

Table 15 includes entries from Registry of Intentions by ECHA and Member States’ authorities for

restriction proposals, proposals for harmonised classifications and labelling and proposals for

identifying Substances of Very High Concern (SVHC). For further description of the Registry of

Intentions and other background information on the legislative framework, see Appendix 1.

According to the information on the ECHA homepage, Annex XV dossiers are submitted for DIPP

and DMEP and both substances are included in the Candidate list.

TABLE 15

SELECTED PHTHALATES IN REGISTRY OF (SVHC) IN TENTION S AS OF AUGUST 2013)

Registry of: CA S No Su bst a nces SV HC

Scope

Dossier

intended

by :

Da t e of

su bmission:

SV HC intentions

A nnex XV

dossiers

su bmitted

605-50-5 Diisopentyl phthalate

(DIPP)

CMR (Repr. 1B) A ustria Su bmitted:

06 /08/2012

117-82-8 Bis(2-methoxyethyl)

ph thalate (DMEP)

CMR (Repr. 1B) Germany Su bmitted:

01/08/2011

Annex XIV recommendations

None of the selected phthalates have been recommended for Annex XIV inclusion (only relevant for

those already included in the candidate list ) in the latest lists of Annex XIV recommendations of 17

January 2013.

2.1.4 Other legislation/initiatives

Denmark

The Ministry of Environment in Denmark has after a finalised consultation period published a

strategy for phthalates in June 2013. The strategy was developed in collaboration with the Ministry

of Health, which has contributed with knowledge about phthalates in medical devices. The strategy

identifies areas where more information is needed and areas where initiatives are required on a

short term basis and in the long term in order to achieve sufficient protection of man and

env ironment. Areas where sufficient information is available for further risk management are also

identified.


In Nov ember 2012 Denmark issued a statutory order, BEK nr 1113, on the ban of certain phthalates

in indoor articles. The order bans the phthalates DEHP, DBP, BBP and DIBP in indoor articles and

articles with direct contact with the skin or mucous membranes. The ban is postponed until 2015 to

allow industry time for the phase-out. The phthalates in question have been associated with

endocrine related endpoints.

According to the Phthalate Strategy, in 2013 the Danish EPA will initiate a screening of information

av ailable on the endocrine disrupting effects of phthalates which have been registered, with the

exception of phthalates which have already been classified as toxic to reproduction, as these are

expected to meet the future EU criteria for identification as endocrine disruptors. Consequently, a

screening will be carried out for 20 phthalates, as six of the registered or pre-registered phthalates

have been classified as toxic to reproduction. The onward process will then be decided, as

substances may be nominated for substance evaluation under the REACH Regulation in order to

procure further documentation, or a proposal for EU legislation (harmonised classification (in case

the ev aluation concludes the effects meet the classification criteria for e.g. reprotoxicity), inclusion

in the Candidate List, restrictions) may be prepared (Danish EPA, 2013).

Sweden

The Swedish Chemicals Agency (KEMI) informs on their website, that the Swedish government has

assigned KEMI to conduct a survey of the use of phthalates suspected to be toxic to reproduction or

endocrine-disrupting and the availability of alternative materials. On the basis of the survey, KEMI

will be working, for instance through industry dialogues, for companies voluntarily to replace these

phthalates with less hazardous substances or materials.

The mandate includes investigating the need and prerequisit es for Sweden to impose national

restrictions on the use of phthalates suspected to be toxic to reproduction or endocrine-disrupting.

Possible ways to act at the EU level should be investigated. The work should take into account

initiatives within the EU to classify, restrict or establish an authorisation process for phthalates.

Any legislative proposals should include an impact assessment and an analysis of the impact on

trade with other countries, as well as a risk assessment.

KEMI is to present its report to the Government Offices (Ministry of the Environment) no later than

30 Nov ember 2014 (KemI, 2013).

2.2 International agreements

Table 16 shows that none of the selected phthalates are covered by the listed international

agreements.

TABLE 16

IN TERN ATIONAL AGREEMEN TS ADDRESSIN G PHTHALATES

A greement Su bst a nces How t he selected ph t h a la t es a re a ddressed

OSPA R Convention Non e of the selected

ph thalates are

cov ered.

Other phthalate esters are included in the list of

Su bstances of Possible concern, Section B (Substances

w hich are of concern for OSPAR but which are

a dequately addressed by EC initiatives or other

in ternational forums)

HELCOM (Helsinki

Con vention)

Same as above

Rot terdam

Con vention (PIC

Con vention)

Same as above


45

A greement Su bst a nces How t he selected ph t h a la t es a re a ddressed

St ockholm

Con vention

Same as above

Ba sel Convention Wa stes from

pr oduction,

formulation and use of

r esins, latex,

pla sticisers,

g lues/adhesives

Th ese wastes are considered hazardous waste under the

pr ov isions of the Basel Convention unless they do not

possess any of the characteristics contained in Annex III

of th is Convention.

Con vention on Long-

range

T ransboundary Air

Pollution (CLRTAP)

Not r elevant

2.3 Eco-labels

Table 17 gives an overview of how selected phthalates are addressed by the EU and Nordic eco-

labelling schemes.

Under the Nordic Swan product criteria, many of the criteria mentioning phthalates exclude the use

of phthalates as a substance group; whereas for some product types hazardous substances with

classification relevant to DIPP, DMEP and in some DEP are not permitted. For the EU flower,

criteria targeting phthalates do generally and explicitly not permit the use of DINP and DIDP,

whereas DIPP and DMEP are not mentioned explicitly but are not permitted due to their

classification.


TABLE 17

ECO-LABELS TARGETIN G SELECTED PHTHALATES

Eco-label A rt icles Crit eria relev a nt for ph t h a la t es Docu m ent t it le

Nordic Swan Dishwasher

detergents

General restriction or ban regarding CMR

classified substances. This requirement includes

ph thalates classified as Repr. 1B (DIPP and

DMEP).

Nor dic Ecolabelling of

Dishwasher detergents,

V ersion 5.3 • 15 December

2 009 – 30 June 2015

De-icers Same as above Nor dic Ecolabelling of De-

icers, Version 2.3 • 18 March

2 004 – 31 December 2014

Cleaning agents for

u se in the food

in dustry

Same as above Nor dic Ecolabelling of

Cleaning agents for use in the

food industry, Version 1.6 • 13

October 2005 – 31 March

2 016

Hand Dishwashing

Detergent

General restriction or ban regarding content of

CMR classified substances or endocrine

disruptors in category I or II. This requirement

in cludes phthalates classified as Repr. 1B (DIPP

a nd DMEP) and DEP included in the EU list of

en docrine disruptors, category I.

General CMR

Nor dic Ecolabelling of Hand

Dishwashing Detergents,

V ersion 5.1 • 21 March 2012 –

31 March 2016

Cosmetic products Same as above Nor dic Ecolabelling of

Cosmetics, Version 2.6 • 12

October 2010 – 31 December

2 014

Cleaning products Same as above Nor dic Ecolabelling of

Cleaning products, Version

5 .0 • 13 March 2013 – 31

Ma rch 2017

La undry detergents

a n d stain removers


La undry detergents and stain

r emovers, Version 7.3 • 15

December 2011 – 31 December

2 015

Ton er cartridges Same as above Nor dic Ecolabelling of

Remanufactured OEM Toner

ca rtridges, Version 5.1 • 15

Ju ne 2012 – 30 June 2016

Ph otographic

dev elopments services

Same as above Nor dic Ecolabelling of digital

Ph otographic developments

services, Version 2.4 • 19


2 014

Pr inting Companies Same as above Nor dic Ecolabelling of

Pr inting companies, printed

m atter, envelopes and other

converted paper products,


47



2 011 – 31 December 2017

Ca r and boat care

pr oducts

Same as above Nor dic Ecolabelling of Car and

boa t care products, Version

5 .1 • 21 March 2012 – 31

Ma rch 2016

La undries/ Textile

Services


La undries/ Textile Services,


2 012 – 31 December 2016

Dishwasher

detergents for

pr ofessional use


Dishwasher detergents for

pr ofessional use, Version 5.3 •

15 December 2009 – 30 June

2 015

La undry detergents

for professional use


La undry detergents for

pr ofessional use,


2 009 – 31 December 2014

Ch emical building

pr oducts

Ph talates must not form part of the product. Nor dic Ecolabelling of

Ch emical building products,

V ersion 1 .6 • 29 May 2008 –

31 October 2014

In door paints and

v arnishes

In gredients classified as acutely toxic in category

I, II a n d II, as resp. sensitisers, as CMR in

ca tegory I or II or as STOT, category I and II

sh all not be used.

On ly phthalates that are risk assessed.

A dditionally DNOP (di-n-octyl phthalate), DINP

(di-isononyl phthalate), DIDP (di-isodecyl

ph thalate) are not permitted in the product.

Nor dic Ecolabelling of Indoor

pa ints and varnishes, Version

2 .3 • 4 November 2008 – 31

Ma rch 2015

Ma chines for parks

a n d gardens

Certain phthalates must (with a few exceptions)

n ot be added to plastic or rubber materials.

Ph thalates include: DINP, DIDP, DEP,

DMEP, a nd DIPP.


Ma chines for parks and

g arden, Version 5.0 • 13 March

2 013 – 31 March 2017

Floor coverings Ph thalates must not be actively added to the

floor covering.

Nor dic Ecolabelling of Floor

cov erings, Version 5.1 • 12


2 014

In dustrial cleaning

a n d degreasing agents

Ph thalates must not be present in the product. Nor dic Ecolabelling of

In dustrial cleaning and

degreasing agents, Version 2.5

• 13 October 2005 – 31 March

2 016

Pa nels for the Ph thalates must not be added to chemical Nor dic Ecolabelling of Panels



bu ilding, decorating

a n d furniture industry

pr oducts and materials including surface

tr eatments.

In a ddition the t otal amount of added chemical

su bstances classified by suppliers as

env ironmentally hazardous, e.g. Aquatic Acute 1

(H400), Aquatic Chronic 1 (H410), , must be

<0.5 g/kg of the panel’s constituent material

(Concerns DIPP, DINP, DIDP).

for the building, decorating

a n d furniture industry,

Fu rniture and

fitments

Ph thalates must not be present in/added to the

ch emical product or material.


Fu rniture and fitments,


3 0 June 2015

Textiles, skins and

leather

Pla stic parts must not contain phthalates.

Phthalates and REACH candidate substances are

a lso forbidden in chemicals in textile processes

following the production of the fibre, such as

spinning, weaving, wet processes (washing,

bleaching and dyeing) and chemicals for coating,

m embranes and laminates


Textiles, skins and leather,


2 012 – 31 December 2016

Ou tdoor furniture and

playground

equ ipment

No ou tdoor furniture or playground equipment

or raw materials may contain phthalates.


Ou tdoor furniture and

playground equipment,

Ba ckground for version 3.

Fa bric cleaning

pr oducts containing

m icrofibres

Ph thalates are prohibited from use in chemical

pr oducts and additives used for the pre-

tr eatment and surface treatment of metals and

pla stics (e.g. coatings) as well as adhesives.

Nor dic Ecolabelling of Fabric

cleaning products containing

m icrofibers, Version 2.1 • 12

October 2010 – 31 March 2016

Toy s Ph thalates shall not be actively added to

pla stic/plastic parts and rubber, be contained in

su rface treatment of plastic/plastic parts, rubber

or metal, or be added to the chemical products

u sed in wood-based materials including surface

tr eatment, or added to glue.

Nor dic Ecolabelling of toys,


31 March 2016

Sa nitary products Polymers or adhesives must not contain

h a logenated organic compounds or phthalates,

ex cept pollutants.


Sa nitary products, Version 5.4

• 5 March 2008 – 31 October

2 015

Disposable bags,

tu bes and accessories

for health care

No plasticisers or other additives added to the

pla stic or substances used in adhesives may have

pr operties categorised in REACH (Registration,

Ev aluation and Authorisation of Chemicals) as

su bstances of very high concern (SVHC) and

similar substances, e.g. EU-listed endocrine

disruptors such as DEP.

Th e phthalates DEHP, BBP, DBP, DINP, DNOP

a n d DIDP may not be used as plasticisers or

oth er additives, nor may they be used in

a dhesives.


Disposable bags, tubes and

a ccessories for health care,

V ersion 1 .4 • 13 December

2 007 – 31 December 2015


49


Compost bins A dditives based on phthalate, may not be

pr esent in the plastic material


Compost bins, Version 2.9 • 7

Ju ne 1996 – 30 June 2014

Closed Toilet System Same as above Nor dic Ecolabelling of Closed

Toilet System, Version 2.8 • 9

A pril 1997 – 30 June 2015

Heat pumps Ph thalates must (with a few exceptions) not be

a dded to chemical products (e.g. cleaning

pr oducts, colours, lacquers, adhesives and

sea lants) and rubber and plastic products.

Ph thalates include: DINP, DIDP, DEP,

DMEP, a nd DIPP.

Nor dic Ecolabelling of Heat

pumps, Version 3.0 • 13 March

2 013 – 31 March 2017

Stov es Ph thalates must not be actively added to

ch emical products such as adhesives, sealants,

cleaning agents, paints and lacquers that are

u sed during the manufacture and surface

tr eatment of the stove.

Nor dic Ecolabelling of Stoves,

V ersion 3.1 • 12 October 2010

– 3 1 October 2014

Ca ndles Ca ndles must not contain phthalates. Nor dic Ecolabelling of

Ca ndles, Version 1 .3 • 13

December 2007 – 30 June

2 015

EU Flower Footwear Ph thalates: Only phthalates that at the time of

a pplication have been risk assessed and have not

been classified with the phrases (or

combinations thereof): R60, R61, R62, R50, R51,

R52, R53, R50/53, R51/53, R52/53 (aquatic

tox icity and toxicity to reproduction, among

oth ers, i.e. (DIPP and DMEP) may be used in

th e product (if applicable). Additionally DNOP

(di-n-octyl phthalate), DINP (di-isononyl

ph thalate), DIDP (di-isodecyl phthalate) are not

permitted in the product.

COMMISSION DECISION

of 9 July 2009

on establishing the ecological

cr iteria for the award of the

Community eco-label for

footwear

In door paints and

v arnishes

Ph thalates: Only phthalates that at the time of




R52, R53, R50/53, R51/53, R52/53 (aquatic


oth ers, i.e. DIPP and DMEP) may be used in

th e product before or during tinting (if

a pplicable). Additionally DNOP (di-n-octyl

ph thalate), DINP (di-isononyl phthalate), DIDP

(di-isodecyl phthalate) are not permitted in the

pr oduct.

COMMISSION DECISION of

13 August 2008

establishing the ecological


Community eco-label to

in door paints and varnishes

Ou tdoor paints and

v arnishes

Ph thalates: Only phthalates that at the time of




COMMISSION DECISION

of 13 August 2008





R52, R53, R50/53, R51/53, R52/53 (aquatic


oth ers, i.e. DIPP and DMEP) may be used in

th e product before or during tinting (if

a pplicable). Additionally DNOP (di-n-octyl

ph thalate), DINP (di-isononyl phthalate),

DIDP (di-isodecyl phthalate) are not permitted

in the product.

Community eco-label to

ou tdoor paints and varnishes

Per sonal computers If a ny plasticiser substance in the manufacturing

pr ocess is applied, it must comply with the

r equirements on hazardous substances set out in

cr iteria 5 and 6 (aquatic toxicity and toxicity to

r eproduction, among others, i.e. DIPP and

DMEP). Additionally DNOP (di-n-octyl


(di-isodecyl phthalate) shall not intentionally be

a dded to the product.

COMMISSION DECISION of 9

Ju ne 2011 on establishing the

ecological criteria for the

a ward of the EU Ecolabel for

per sonal computers

Notebook computers Same as above COMMISSION DECISION

of 6 June 2011

on establishing the ecological


EU Ecolabel for notebook

computers

Wooden floor

cov erings

Th e requirements of part 2.1 on dangerous

su bstances for the raw wood and plant

tr eatments shall also apply for any phthalates

u sed in the manufacturing process (aquatic


oth ers, i.e. DIPP and DMEP). Additionally

DNOP (di-n-octyl phthalate), DINP (di-isononyl

ph thalate), DIDP (di-isodecyl phthalate) are not

permitted in the product.


2 6 November 2009 on



Community Ecolabel for

w ooden floor coverings.

Textile floor coverings If a ny plasticizer substance in the manufacturing

pr ocess is applied, only phthalates that at the

t ime of application have been risk assessed and

h ave not been classified with the phrases (or

combinations thereof) may be used: R50 (very

tox ic to aquatic organisms), R51 (toxic to aquatic

or ganisms), R52 (harmful to aquatic organisms),

R53 (may cause long-term adverse effects in the

a quatic environment), R60 (may impair

fer tility), R61 (may cause harm to the unborn

ch ild), R62 (possible risk of impaired fertility).

A lternatively, classification may be considered

a ccording to Regulation (EC) No 1272/2008. In

th is case no substances or preparations may be

a dded to the raw materials that are assigned, or

m ay be assigned at the t ime of application, with

a n d of the following hazard statements (or





Community Ecolabel for

textile floor coverings


51


combinations thereof): H400, H410, H411,

H412, H413, H360F, H360D, H361f, H361d

H360FD, H361fd, H360Fd, H360Df.

A dditionally DNOP (di-n-octyl phthalate), DINP

(di-isononyl phthalate), DIDP (di-isodecyl

ph thalate) are not permitted in the product

Wooden furniture If a ny plasticizer substance in the manufacturing

pr ocess is applied, phthalates must comply with

th e requirements on hazardous substances set

ou t in section 2 (aquatic toxicity and toxicity to


DMEP). Additionally DNOP (di-n-octyl


(di-isodecyl phthalate) are not permitted in the

pr oduct.





Community eco-label for

w ooden furniture.

Light bulbs If a ny plasticizer substance in the manufacturing

pr ocess is applied, it must comply with the

r equirements on hazardous substances set out in

Cr iteria 5 and 6 (aquatic toxicity and toxicity to


DMEP). Additionally, DNOP (di-n-octyl

ph thalate), DINP (di-isononyl phthalate) and

DIDP (di-isodecyl phthalate) shall not

in tentionally be added to the product.

COMMISSION DECISION of 6

Ju ne 2011 on establishing the

ecological criteria for the


light source

Pr inted paper Th e following substances or preparations shall

n ot be added to inks, dyes, toners, adhesives, or

w ashing agents or other cleaning chemicals used

for the printing of the printed paper product:

— Ph thalates that at the t ime of application are

classified with risk phrases H360F, H360D,

H361f (toxic to fertility; i.e. DIPP and DMEP)

in accordance with Regulation (EC) No

1 272/2008


1 6 August 2012 establishing

th e ecological criteria for the


pr inted paper

2.4 Sum m ary and conclusions

DIPP and DMEP are subject to harmonised CLP classification and are classified for reproductive

toxicity in category 1 B. In addition, DIPP is classified as acute toxic 1 in aquatic environments.

The majority of industry notifiers do not suggest a classification for the selected phthalates without

a harmonised classification due to lack of sufficient data. Besides classification proposals for acute

toxicity, skin and eye irritation, and acute aquatic toxicity for some of the substances the most

serious classification proposals suggested include classification for reproductive toxicity in category

2 for DEP suggested by 2 notifiers out of 7 0 and for DINP (CAS no. 68515-48-0) suggested by 3

notifiers out of 269. Specific target organ toxicity – single and repeated exposure is suggested for

DEP by 9 and 10 out of 7 0 notifiers. One has suggested a classification as a skin irritant. Chronic

aquatic toxicity in category 4 is suggested for DINP (CAS no. 28553-12-0) by 28 out of 857 notifiers

and chronic aquatic toxicity in category 1 and 2 is suggested for DIDP (CAS no. 26761-40-0) by 23

and 43 notifiers respectively.


EU legislation restricts the use of DINP and DIDP in toy s and childcare articles which can be placed

in the mouth by children and prohibits the use of DMEP and DIPP in cosmetic products. Specific

EU labelling requirements apply to certain medical devices containing phthalates classified as

reproductive toxicants in category 1 and 2. A ban on CMR substances in a concentration above the

classification limits in toys also apply to DMEP and DIPP as well as requirements for labelling for

certain medical devices. EU also restricts the use of DINP and DIPD in plastic materials intended to

come into contact with food.

Denmark has issued a national ban on the import, sale and use of phthalates in toys and childcare

articles for children aged 0-3 years if the products contain more than 0.05 per cent by weight of

phthalates. Other national legislation addresses the maximum concentration of phthalates in water

leaving the water works and in consumer tap water. In addition , DEP has a defined occupational

exposure limit.

DIPP and DMEP are included in the Candidate List under the REACH Regulation and thus in the

line for being subject to the authorisation process.

The Swedish Chemicals Agency plans to investigate the need for national restrictions on phthalates

toxic to reproduction or endocrine-disrupting.

Phthalates are generally not addressed directly in international agreements. However, hazardous

wastes from production, formulation and use of plasticisers, falls under the provisions of the Basel

Conv ention.

Phthalates are addressed by EU and Nordic eco-labelling schemes, in numerous product types

either directly (“phthalates”, DINP, DIDP) or by means of their classification (DEP, DIPP and

DMEP).


53

3. Manufacture and uses

3.1 Manufacturing

Manufacturers of phthalates and other plasticisers in the EU are organised in the European Council

for Plasticisers and Intermediates (ECPI). The organisation has a membership of eight companies

inv olved in the production of plasticisers. Some of the manufacturers of phthalates in the EU are

not members of the organisation. ECPI prov ides some overall information on the use of the

phthalates on the website "Plasticisers and flexible PVC information centre" (ECPI, 2013a). The

organisation has been contacted in order to obtain updated information on the manufactured

v olumes and use of the six phthalates. ECPI (2013e) has responded that they cannot give

production volumes and have given information on the status of the phthalates in question in the

EU (see descriptions in relevant sections below).

Manufacturing processes

According to ECPI (2013a) DIDP, DINP and DPHP are produced by esterification of "oxo" alcohols

av eraging a carbon chain length of nine or ten. The "oxo" route differs from the 2 -ethylhexanol

route in that the alcohol for subsequent esterification is produced through the hydroformylation of

an alkene (olefin; rather than the dimerisation of butyraldehyde). The hydroformylation process

adds one carbon unit to an alkene chain by reaction with carbon monoxide and hydrogen under

specific temperature and pressure conditions and with the help of a catalyst. In this way a C8 olefin

(alkene) is carbonylated to yield a C9 alcohol; a C9 alkene is carbonylated to produce a C10 alcohol.

Due to the distribution of the C=C double bonds in the olefin and differences in catalysts selectivity,

the position of the added carbon atom can vary, as is the case for DINP and DIDP. In such a

reaction, an isomer distribution is generally created (e.ei. with varying physical and chemical

structure), with the precise nature of this distribution being dependent upon the precise reaction

conditions. Consequently, these alcohols are termed iso-alcohols and subsequently iso-phthalates.

(ECPI, 2013a).

DINP - Isonony l alcohol, used in the synthesis of DINP, is produced via either the dimerization of

butene or the oligomerization of propylene/butene. DINP is produced by esterification of phthalic

anhydride with isononyl alcohol in a closed system. The reaction rate is accelerated by elevated

temperatures (140-250 °C) and a catalyst. Following virtually complete esterification, excess alcohol

is removed under reduced pressure and the product is then typically neutralised, water washed and

filtered (ECPI, 2013b).

DIDP - DIDP is according to the EU Risk Assessment prepared from propylene and butenes

through an oligomerisation process forming hydrocarbons with 8 to 1 5 carbon atoms (EC, 2003a).

After distillation (in view of obtaining nonene), oxonation forms aldehydes with one more carbon

atom (“isodecanal”). The latter are hydrogenated and distilled to form monohydric alcohols (mainly

C1 0). These are reacted with phthalic anhydride (PA). The first reaction step, alcoholysis of PA to

giv e the monoester, is rapid and goes to completion. By charging in excess alcohol and by removing

the water which is formed, the equilibrium can be shifted almost completely towards the products

side. The reaction rate is accelerated by using a catalyst and high temperature. Depending on the

used catalyst the temperature range is in between 140°C and 250°C. For an acid catalyst,

neutralisation with aqueous caustic soda or sodium carbonate is necessary. However, traces of


alkali remain in the organic phase, and therefore a washing step is included. After distillation of

remaining water and alcohol the catalyst is removed by filtration.

Information on the manufacture of the other phthalates has not been identified.

Manufacturing sites

Specific information on manufacturing sites in the EU has not been searched for.

DINP is produced by four companies within the EU: BASF AG (Germany), Evonik Oxeno GmbH

(Germany), ExxonMobil Chemical (Belgium), Polynt (Italy) (ECPI, 2013b).

DIDP is produced by two companies within the EU: ExxonMobil Chemical (Belgium) and Polynt

(Italy) (ECPI, 2013c) while DPHP is produced by BASF (Germany) and Perstorp Oxo AB (Sweden)

(ECPI, 2013b).

DIPP is registered by one company only , Eurencu Bofors AB (likely an importer; the company

produces explosives), but may be imported or manufactured by other companies in smaller

quantities.

DEP is registered by 5 companies, among these one of the major manufacturers of phthalates:

Poly nt (Italy) and Proviron (Belgium).

DMEP is not registered under REACH.

3.1.1 Manufacturing volumes

All six selected phthalates are pre-registered substances under REACH and listed in Table 18 with

an indication of registered tonnage bands and names of companies which have registered the

substances (manufacturers or importers).

Substances registered with ECHA: The database on registered substances includes as of June

2013:

substances manufactured or imported at 100 tonnes or more per year (deadline 31st May

2013),

substances which are carcinogenic, mutagenic or toxic to reproduction with manufacture or

import above 1 tonne per year (Deadline for registration was 30 November 2010)"

Three of the substances DINP, DIDP and DPHP are manufactured or imported in the 100,000-

1 ,000,000 t/y tonnage band; DEP in the 1,000-10,000 t/y tonnage; DIPP in 1 0-100 t/y. DMEP is

not registered indicating that the manufactured and imported volume is less than 1 t/y or that there

is no intention to market the substance in Denmark.


55

TABLE 18

REGISTERED TON N AGE OF THE SIX PHTHALATES AS OF 20 JU NE 2013

CA S No EC No Su bst a nce na m e A bbreviat ion Regist ered,

t onnage ba nd ,

t /y *1

Regist ra nt s

84-66-2 2 01-550-6 Diethyl phthalate DEP Full: 1,000-10,000

In termediate Use

On ly

COIM SpA, IT

La piz Europe Limited, UK

POLYNT S.p.A.

Pr ov iron Basic Chemicals nv

Su stainability Support

Services (Europe) AB

GRACE Catalyst AB, SE

GRACE GmbH & Co. KG, DE

605-50-5 2 10-088-4 Diisopentyl phthalate DIPP 1 0-100 EURENCO Bofors AB, SE

53306-54-0 2 58-469-4 Bis(2-propylheptyl)

ph thalate

DPHP 1 00,000-

1 ,000,000

A RKEMA FRANCE, FR

BA SF SE, DE

DEZA a.s., CZ

Grupa Azoty Zakłady, PO

Per storp Oxo, SE

POLYNT S.p.A., IT

117-82-8 2 04-212-6 Bis(2-methoxyethyl)

ph thalate

DMEP Not r egistered

68515-48-0

28553-12-0

27 1-090-9

2 49-079-5

1 ,2-


a cid, di-C8-10-

br anched alkyl esters,

C9 -rich

Di-''ison onyl''

ph thalate

DINP-1

DINP-2

1 00,000-

1 ,000,000

1 00,000-

1 ,000,000

Ex x onMobil Chemical, NL

BA SF SE, DE

DEZA a.s., CZ

DOW BENELUX B.V.,NL

Ev onik Industries AG, DE

Ev onik Oxeno GmbH, DE

In st ituto Suizo para el

Fom ento de la Seguridad-

Sw issi España S.L.U., ES

KTR Europe GmbH, DE

POLYNT S.p.A., IT

REA CH GLOBAL SERVICES

S.A., BE

68515-49-1

26761-40-0

27 1-091-4

2 47-977-1

1 ,2-


a cid, di-C9-11-

br anched alkyl esters,

C10-rich

Di-''isodecyl''

ph thalate

DIDP-1

DIDP-2

1 00,000-

1 ,000,000

Not r egistered

Ex x onMobil Chemical,NL

In fineum UK Ltd, UK

*1 A s indicated in the lists of pre-registered and registered substances at ECHA’s website.

In the production statistics of Eurostat all phthalates, apart from dibutyl (mainly DBP) and dioctyl

(mainly DEHP), are included in one group with a total production in 2011 of approximately

7 80,000 t/y whereas the average for the period 2006-2010 was approximately 870,000 t/y (Table

1 9).


TABLE 19

EU27 PRODUCTION OF SELECTED PHTHALATES (EUROSTAT, 2012A)

Product

code

T ext Produ ct ion , t /y

A vera ge 2006-

2010

2011

20143410 Dibutyl and dioctyl orthophthalates 27 8,416 1 46,333

20143420 Other esters of orthophthalic acid 8 65,573 7 82,533

According to ECPI, the consumption of DINP, DIDP and DPHP (di-2-propylheptyl phthalate), has

increased from representing about 50% of total phthalate sales in Europe in 2001 to approximately

83% of the total sales in 2010 (COWI et al., 2012). In Europe, about one million tonnes of

phthalates were manufactured in 2010 (COWI et al., 2012).

DINP and DIDP

As background for an assessment of DINP and DIDP prepared by ECHA in 2011, a report on the

v olumes of DINP and DIDP was prepared which presents the most current ov erview of publicly

av ailable information on the manufacture and use of DINP and DIDP (COWI et al., 2012). The

ov erall flow of the sum of DINP, DIDP and DPHP is shown in Figure 1. As shown, the EU is a net

exporter of these substances DINP and DIDP, both as regards the substances as such and in articles.

These data are further discussed in the next section.

FIGURE 1

SCHEMATIC VIEW OF THE APPROXIMATE FLOW OF DINP, DIDP AND DPHP IN EU IN 2010 (BASED ON COWI ET AL.,

201 2)

Global manufacture of the substances

DINP, DIDP and DPHP account for a major part of the plasticiser market in Europe than in other

parts of the world, which influence to what extent the substances are imported in articles from

countries outside the EU.

The most recent available estimate of the use of plasticisers by region, presented at the 22 nd Annual

Vinyl Compounding Conference in July 2001, concerns 2010 (Calvin, 2011). The breakdown of the

plasticiser market in Western Europe, USA and Asia is shown in Table 20. According to this

presentation, DINP/DIDP represented 63% of the plasticiser market in Western Europe in 2010,

whereas it only represented 33% of the market in the USA and 21% of the market in Asia. The total


57

global market for plasticisers was estimated at 6 million tonnes, with 1 .4 million tonnes in Europe,

the Middle East and Africa, 1.1 million tonnes in the Americas and 3 .5 million tonnes in Asia

(Calvin, 2011). Of the global plasticiser market, phthalates represented 84% (Calvin, 2011).

As shown in the table, the on-going substitution of the traditional main general plasticiser DEHP

has not reached the same level in Asia as in Europe and the USA. Also, non-phthalate plasticiser

and “linears/other phthalates” are used to a higher extent in the USA than in Europe. This may, at

least partly, be because non-ortho-phthalates like terephthalates (for example DEHT) were

traditionally produced and used to a higher extend in Nor th America.

TABLE 20

W ORLD PLASTICISER MA RKET 201 0 (CALVIN, 201 1)

Pla sticiser Percent a ge of t ot a l pla st iciser m a rket *1

West ern Eu rope USA A sia

DEHP 1 6 1 9 6 0

C9/C10 phthalates *2 6 3 3 3 2 1

Linears/other phthalates

*3

6 1 9 9

Non phthalates 1 6 3 8 1 0

T otal 1 00 1 00 1 00

*1 Th e data are indicated to be based on two market reports (SRI,CMAI) and BASF estimates.

*2 Note of the authors of this survey: Mainly DINP (C9) and DIDP/DPHP (C10).

*3 Note of the authors of this survey: The three other phthalates subject of this survey will be included in this

g r oup.

3.2 Im port and export

3.2.1 Import and export of selected phthalates in Denmark

The import of all phthalates as retrieved from Statistics Denmark is shown in the table below. In

Denmark, the production statistics uses the same CN8 nomenclature as used for the import/export

statistics. The table includes import, export and production statistics for all phthalates. Phthalates

are however not produced in Denmark.

As the registered trade seems to have an inconsequent use of commodity codes, data for all codes

relevant to phthalates (on their own) are presented in the table. DINP, DIDP and DPHP would be

expected to be included in the commodity group "Diisooctyl, diisononyl and diisodecy l

orthophthalates". The imported quantities, indicate however that the substances are more likely

included in the group "Dinonyl or didecyl orthophthalates". The dinonyl orthophthlates (C9)

includes DINP and this substance accounts for the main part of the C9 phthalates. Other phthalates

that might be included under this CN8 code is 911P (linear nine-eleven phthalate, slightly branched)

and 7 9P (linear seven-nine phthalate (highly branched)) (COWI et al., 2012). The didecyl

orthophthlates (C10) may include DIDP and this substance accounts for a major part of the C10

phthalates. Other phthalates that might be included under this CN8 code are DPHP, 1 012P (linear

ten-twelve phthalate) and 610P (linear six-ten phthalate).

The other three selected phthalates are expected to be included in an aggregated commodity groups

"Esters of orthophthalic acid (excl. dibutyl, dioctyl, dinonyl or didecyl orthophthalates)".


TABLE 21

DAN ISH PRODU CTION, IMPORT AND EXPORT OF ALL PHTHALATES (IMPORT/EXPORT FROM EU ROSTAT, 2012A;

PRODU CTION STATISTICS FROM STATISITICS DEN MARK, 201 2)

CN8 code T ext Im port , t /y Export , t /y Produ ct ion , t /y

A v era ge

2007-2011

2012 A v era ge

2007-2011

2012 A v era ge

2007-2011

2012

29173100 Dibutyl orthophthalates 0 0 0 0 0 0

29173200 Dioctyl orthophthalates 1 ,239 8 89 2 26 5 9 0 0

29173300 Din onyl or didecyl

orthophthalates

1 ,573

1 ,355 8 23 7 10 0 0

29173400 Esters of orthophthalic

a cid (excl. Dibutyl,

dioctyl, dinonyl or

didecyl orthophthalates)

0 1 02 0 1 2 0 0

29173410 Diisooctyl, diisononyl

a n d diisodecyl

orthophthalates

8 0 13 0 0 0

3.2.2 Import and export of the selected phthalates in EU

Statistics on manufacture and import/export of selected phthalates on their own

EU external trade in tonnes of all phthalates on their own is shown in the Table 22. As indicated

abov e for import to Denmark, DINP, DIDP and DPHP are most probably included in the group of

"Dinony l or didecyl orthophthalates", with a total export of 260,000 t/y (from EU) in 2011 while the

import was approximately 20,000 t/y in 2011 i.e. the net export was approximately 240,000 t/y.

DINP, DIDP and DPHP are expected to account for nearly 100% of the reported import and export,

with DINP likely representing the majority.

The three other phthalates are included in an aggregated commodity group (“Esters of

orthophthalic acid (excl. cibutyl, dioctyl, dinonyl or didecyl orthophthalates”) and the import export

data cannot be extracted from the statistics. As expected, the import and export numbers for this

aggregate group are however smaller than the imports and exports of DIDP/DINP/DPHP (“ Dinonyl

or didecy l orthophthalates”), which are today the key general plasticisers as described above. Again

there is however a net export, signalling the EU’s position as a key producer of phthalates globally.


59

TABLE 22

EU 27 EXTERN AL IMPORT AND EXPORT OF ALL PHTHALATES (EU ROSTAT, 201 2A)

CN code T ext Im port , t /y Export , t /y

A v era ge

2006-

2010 *1

2011* A v era ge

2006-

2010 *1

2011*

2917.3100 Dibutyl orthophthalates 2 9 8 : 4 ,8 6 4 :

2917.3200 Dioctyl orthophthalates 5 ,2 1 8 4 ,7 1 6 5 3 ,002 3 1 ,8 7 2

2917.3300 Din onyl or didecyl orthophthalates 1 7 ,4 7 1 1 9 ,8 3 8 1 5 1 ,1 8 8 2 60,5 06

2917.3400 Esters of orthophthalic acid (excl.

cibutyl, dioctyl, dinonyl or didecyl

orthophthalates)

3 ,1 2 9 *1 - 7 1 ,1 8 1 *1 -

2917.3410 Diisooctyl, diisononyl and diisodecyl

orthophthalates

7 3 9 1 ,2 01 7 ,3 01 8 6 4

*1 Av erage for those years where data are reported.

As part of background document for ECHA's DINP/DIDP assessment, an est imate of the

import/export of DIDP and DINP with articles was performed. The methodology applied was

based on a methodology developed for the Danish EPA (Skårup and Skytte, 2003). The results are

shown in Table 23.

The total plasticiser content of both imported and exported products (articles) was estimated at

about 170,000 t/y. For the estimate of import/export of DINP/DIDP in articles it was be assumed

that DINP/DIDP accounted for the following percentages of the total plasticiser consumption by

region: EU, Switzerland, Norway, Iceland: 63%; the Americas: 33%; Asia and rest of the world: 21%.

Assuming DINP/DIDP accounted for the percentages indicated above of the total plasticiser

content, the import and export is estimated at 45,000 tonnes and 105,000 tonnes respectively, and

the export corresponds to about 15% of the total use of DINP/DIDP for manufacturing of products

with plasticisers in the EU.

Of the import into the EU, 51% of the tonnage of the articles originates from China, whereas only

9% of the imported DINP/DIDP (on their own) is estimated to originate from China.

It should be noted that some import/export may take place with articles not covered by the

assessment (e.g. vehicles and electrical and electronic equipment), and the total tonnage imported

in these articles are considered to add some 1 0-30% to the totals, as the major application areas are

cov ered by the statistics.

As a best estimate, adding 20% to the numbers in Table 23, the import of DINP/DIDP (should likely

be considered as including the third key general plasticiser DPHP) in articles was be estimated at

approximately 50,000 tonnes and the export at 125,000 tonnes.


TABLE 23

ESTIMATED DIN P/DIDP CON TENT OF EU27-EXTRA TRADED ARTICLES. AVERAGE OF THE YEARS 2008-201 0 (COW I

ET AL, 201 2)

Product group T on na ge produ ct s

t /y

T on na ge pla st iciser

t /y

T on na ge DINP/DIDP

t /y

Im port Export Im port Export Im port Export

Hoses and profiles 2 1 ,5 7 2 3 8 ,7 2 7 3 ,5 1 5 7 ,5 01 1 ,2 6 3 4 ,4 3 7

Flooring and wall covering 1 2 7 ,1 8 7 2 3 1 ,5 9 2 1 0,5 6 9 2 9 ,8 3 0 2 ,3 9 6 1 8 ,9 9 3

Film/sheets and coated

products

1 ,1 6 4 ,7 7 9 9 2 2 ,2 8 8 7 5 ,2 01 6 8 ,5 7 8 2 1 ,5 05 4 2 ,7 06

Coa ted fabric and other

products from plastisol

2 8 3 ,1 5 1 6 9 5 ,2 3 5 3 ,4 2 6 5 ,9 8 6 9 2 7 3 ,7 4 9

Wires and cables 1 1 7 ,03 6 1 5 3 ,6 7 5 8 ,1 8 3 9 ,6 9 5 2 ,3 3 6 5 ,7 8 0

Mou lded products and other 4 4 9 ,7 5 6 4 7 5 ,3 03 6 3 ,4 4 8 4 7 ,006 1 5 ,05 8 2 9 ,3 6 4

T otal 2 ,1 6 3 ,4 8 2 2 ,5 1 6 ,8 2 0 1 6 4 ,3 4 2 1 6 8 ,5 9 7 4 3 ,4 8 5 1 05 ,02 9

Similar numbers for the other phthalates assessed here; DEP, DIPP, DMEP have not been found.

3.3 Use

3.3.1 Use in the EU

DINP, DIDP and DPHP

DINP, DIDP and DPHP (with DINP as the major) have over the last decade taken over as primary

plasticiser for a major part of the former applications of DEHP. A s a consequence of the different

properties of the three substances, some differences in the use by application are seen.

DINP – DINP is a general plasticiser, which is applied in many products as the direct alternative

for DEHP, the formerly major general PVC plasticiser. As such DINP has a high consumption and is

probably the plasticiser which can be found in most flexible PVC products today. DINP has a wide

range of indoor and outdoor applications. DINP is a commonly used plasticiser, 95% of which is

used for flexible PVC used for construction and industrial applications, and durable goods (wire and

cable, film and sheet, flooring, industrial hoses and tubing, footwear, toys, food contact plastics).

More than half of the DINP used in non-PVC applications involves polymer-related uses (e.g.

rubbers). The remaining DINP is used in inks and pigments, adhesives, sealants, paints and

lacquers (where it also acts as a plasticiser) and lubricants (ECPI, 2013b).

DIDP - DIDP is a common phthalate plasticiser, used primarily to soften PVC. DIDP has properties

of v olatility resistance, heat stability and electric insulation and is typically used as a plasticiser for

heat-resistant electrical cords, leather for car interiors, and PVC flooring. (ECPI, 2013c). Non-PVC

applications are relatively small, but include use in anti-corrosion and anti-fouling paints, sealing

compounds and textile inks.

DPHP - DPHP is often used as an alternative (to DIDP) because only minor compound changes are

needed to adapt wire formulations for example to DPHP (ECPI, 20 13d). It similarly matches DIDP

performance in automotive applications. Its weather resistance makes it a strong candidate for

outdoor applications (ECPI, 2013d). DPHP boasts better UV stability than most general -purpose

plasticisers, making it especially suitable for applications like roofing, geomembranes, or tarpaulins.

Almost all DPHP is used as a plasticiser to make PVC soft and flexible.


61

A total breakdown of the consumption by application in the EU of the three phthalates is not

av ailable. COWI et al. (2012) produced a best available scenario for the breakdown of the

consumption by 2015 based on the available data from industry. According to the data source, it

was however not possible to ev aluate how well these estimates reflect the actual situation in Europe,

but no objections to the breakdown from industry were provided.

TABLE 24

SCEN ARIO FOR THE BREAKDOW N OF THE CON SUMPTION OF DINP AND DIDP BY APPLICATION AREA IN 201 5 (ECHA,

201 2)

Process Application area DINP +DIDP DINP DIDP

Percentage

of total

Consumption,

tonnes

Percentage

of total

Consumption,

tonnes

Percentage

of total

Consumption,

tonnes

Calendering

Fi l m, sheet and coated

pr oducts

1 4.9 1 09,1 7 8 1 1 .5 57 ,01 8 22.0 52,1 40

Fl oor ing, r oofing, w all

cov ering

3.3 24,339 1 .6 7 ,7 39 7 .0 1 6,590

Extrusion

Hose and pr ofile 5.0 36,856 5.1 25,006 5.0 1 1 ,850

W i r e and cable 27 .3 1 99,580 1 7 .3 85,7 61 48.0 1 1 3,7 60

Cl ear , medical, film 6.7 49,37 3 8.1 39,901 4.0 9,480

Injection

moulding

Footw ear and

mi scellaneous

7 .9 57 ,7 1 8 9.7 48,249 4.0 9,480

Plastisol spread

coating

Fl oor ing 1 0.0 7 3,01 7 1 3.8 68,299 2.0 4,7 40

Gener al (coated fabric, wall

cov ering, etc.)

1 0.8 7 9,27 6 1 5.5 7 6,933 1 .0 2,37 0

Other plastisol

applications

Car undercoating and

seal ants

7 .2 52,850 1 0.2 50,498 1 .0 2,37 0

Sl ush/r otational moulding

etc.

1 .8 1 3,21 3 2.2 1 0,845 1 .0 2,37 0

Mixture

formulation N on-PVC applications

5.0 36,600 5.0 24,7 50 5.0 1 1 ,850

Total 1 00.0 7 32,000 1 00 495,000 1 00 237 ,000

Note: The values above have been calculated without rounding. The fact that the figures are calculated to the

n earest tonne does not mean that they should be interpreted as precise to the nearest tonne.

DINP, DIDP and DPHP are typically used as primary plasticisers in PVC, sometimes in combination

with other plasticisers. The actual concentrations are quite variable and depend on the desired

properties of the final PVC. Actual analyses of plasticisers in different products demonstrate that,

for the same product, often different combinations of plasticisers are found. The combination of

plasticisers in a PVC material is partly governed by the desired performance characteristics of the


materials.

Examples of actual measurement of DINP and DIDP from surveys of the substances in products are

listed in Table 25 based on COWI et al. (2012).


Sev eral of the surveys have been undertaken as part of the Danish EPA’s programme on consumer

products (Tønning et al., 2009; Müller et al., 2006; Nilsson et al., 2006; Pors and Fuhlendorf,

2001; Poulsen and Schmidt, 2007, Svendsen et al., 2007). A number of other surveys of the

programme published in 2010 address phthalates in different product groups, but these surveys

have not included DINP and DIDP or other of the phthalates subject to the present survey. DIPP,

DPHP and DMEP have not been included in any of the surveys of the programme on consumer

products, while a few surveys have included DEP as mentioned below.

The EU risk assessment for DINP does not indicate the typical content of DINP in flexible PVC. The

substance is typically used as a 1 :1 substitute for DEHP. According to the EU Risk Assessment for

DEHP, the typical concentration of DEHP v aries, but is often around 30% (w/w).

According to information from ECPI (2013c) the typical content of DIDP in flexible PVC products is

between 25 and 50% (w/w).

The background data report for an Annex XV restriction dossier for DEHP, BBP, DBP and DIBP

prov ides the following data specifically on the use of DINP and DIDP as collected from

manufacturers of different articles (Højbye et al., 2011). The information from this report,

supplemented by information provided by ECPI for the study of COWI et al. (2012) leads to the

following conclusions to be made (cited from COWI et al., 2012):

"DINP is the major plasticiser for plastisol applications, in particular for the production of

flooring products. Plasticiser concentrations vary quite extensively depending on flooring

type. 10-20% plasticiser content, depending on product type, has been reported for products

for the professional market, while higher concentrations (25 -30%) are reported for low -price

cushioned PVC flooring for the private market. I t is not specifically indicated whether the

lower plasticiser content in the products for the professional market is correlated with a

lower flexible PVC content of the flooring.

German investigations performed in 2003 (Stiftung Warentest, 2003 as cited by Hø ibye et

al., 2011) revealed a rather complex picture regarding plasticiser usage in flooring. PVC

flooring marketed in Germany contained one or more of the following phthalates: DIBP,

DBP, BBP, DEHP, DINP, DIDP, DIHP and DIOP. DINP and DIDP were found in significant

concentrations. A total of 25 different products were analysed. The total concentration of

phthalates registered in the products was in the range of 6.3% to 36.5%. According to ECPI,

vinyl floors produced nowadays are based on DINP as the general purpose plasticizer and

use a secondary fast fusing plasticizer, often esters of benzoic acid. DEHP, DIBP, DBP, DIHP

and BBP have been phased out by European flooring manufacturers in the last 3 to 5 years.

They may still be detected in vinyl floorings including a high level of recycled content or in

some flooring produced outside the EU.

DINP is the main plasticiser used in wallpaper/wall covering. According to major producers

of PVC wallpaper, typical plasticiser concentrations are 25 -30%.

One producer has reported DINP concentrations in air mattresses of 20-30%.

Typically, swimming pool liners made of flexible PVC contain 20-30% DINP and pool covers

contain 25-30 % DEHP.

DEHP is the preferred plasticiser in bathing equipment with concentrations in the range 20-

40%. Alternatively 20-30% DINP is used.

DIDP and DEHP are likely the main plasticisers used for cables in the EU. According to one

manufacturer, DIDP constitutes about 80% of the current plasticiser consumption for cables

in the EU. Typical plasticiser concentrations in the PVC insulation are reported at 20-30%.

(According to information provided by ECPI for this study [COWI et al., 2012] , DINP is

rarely used for cables)"


63

TABLE 25

EXAMPLES OF ACTU AL MEASU REMEN T OF DINP AN D DIDP IN PRODUCTS (COW I ET AL., 201 2)

Product group n *1 Number of sa m ples

with substance > 1%*2

DINP con t ent

% (w/w)

DIDP con t ent

% (w/w)

Yea r Orga nisa t ion Sou rce

(plea se find fu ll

reference in COWI et al.,

2012)

DINP DIDP Ra nge A v era ge Ra nge A v era ge

Pa ckaging for

sh ampoo and bath

soa p

1 0 4 n .a. 1 -31 2 2 n .a. n .a. 2 006 Da n ish EPA Pou lsen and Schmidt, 2007

Era sers 2 6

(10) *3

3 n .a. 37 -7 0 47 n .a. n .a. 2 006 Da n ish EPA Sv endsen et. al. 2007

Sex t oys 15 2 n .a. >5 0-60 55 n .a. n .a. 2 005 Da n ish EPA Nilsson et al., 2006

Sex t oys 7 1 1 8 8 6 -7 7 3 9 1 0-55 27 2 009 Th e Netherlands

Food and

Consumer Product

Sa fety Authority

V WA, 2009

T oys for animals 13 1 0 n .a. 7 -54 2 8 n .a. n .a. 2 005 Da n ish EPA Mü ller et al., 2006

T oys and baby articles 2 52 2 3 4 0.7 -41 2 9 9 -32 2 4 2 007 *8 Biedermann-Brem et al.,

2 008

T oys*6 2 05 4 5 1 2 1 -7 5 4 1 1 -11 3 2 008 *7 FCPSA, 2009

Ch ildcare articles *6 2 5 2 1 4 -28 1 6 2 5 2 5 2 008 *7 - “ -

T oys *6 2 58 3 6 31 1 -58 2 8 2 -38 8 2 009 *7 FCPSA, 2010

Ch ildcare articles *6 13 2 0 37 -56 47 - - 2 009 *7 - “ -

Mitten labels 2 2 n .a. 8 -9 8 n .a. n .a. 2 008 Da n ish EPA Tønning et al., 2009

Sh ower mat 7 1 n .a. 1 4 1 4 n .a. n .a. - “ - - “ - - “ -

Soa p packaging 6 1 n .a. 9 9 n .a. n .a. - “ - - “ - - “ -

Pla stic shoes 27 1 1 3 3 1 1 2 009 Sw edish Society

for Nature

Con servation

SSNC, 2009

Con veyer belts 1 2 1 0 2 .5 2 .5 0 0 2 008/

2 009

Da n ish Veterinary

a n d Food

A dministration

DV FA, 2010

Flooring 5 2

*4 5 -31

1 8

*4 *4 2 000 Da n ish EPA Por s and Fuhlendorf, 2001

PV C gloves 4 1 *4 5 9 5 9 *4 *4 - “ - - “ - - “ -


Product group n *1 Number of sa m ples

with substance > 1%*2

DINP con t ent

% (w/w)

DIDP con t ent

% (w/w)

Yea r Orga nisa t ion Sou rce

(plea se find fu ll

reference in COWI et al.,

2012)

DINP DIDP Ra nge A v era ge Ra nge A v era ge

V inyl wallpaper 4 2 *4 2 3-26 2 5 *4 *4 - “ - - “ - - “ -

Ca rpet tiles 2 1 *4 27 27 *4 *4 - “ - - “ - - “ -

Sh oulder bags,

(t ransparent plastic,

cloth like, artificial

leather)

3 1 *4 11 11 *4 *4 - “ - - “ - - “ -

PV C gloves n .i n .i n .i 3 2 3 2 2 000 *9 Sa uvegrain and Guinard,

2 001

Gloves n .i. n .i. n .i. 4 1-43 4 2 1 6-17 17 n .i. In st itute for

Ch emical and

Bioengineering

Wormuth et al., 2006

Pa ints n .i. n .i. n .i. 0 .05-0.5 0.3 0.03-0.3 0.2 n .i. - “ - - “ -

A dhesives n .i. n .i. n .i. 3 -6 *5 4 0.5-6 2 n .i. - “ - - “ -

*1 Number of samples

*2 Number of samples with concentration above a certain level defined in the studies (typically 1 % w/w)

*3 1 0 out of 26 erasers were made of PVC; of these 3 contained DEHP.

*4 Th e data indicated for DINP is the sum of DINP and DIDP

*5 Th e paper indicates the min at the same magnitude as the max – here the min is adjusted on the basis of the indicated mean and max.

*6 Number of samples indicate materials with more than 0.1% of the substances.

*7 Th e Food and Consumer Product Safety Authority, the Dutch Ministry of Agriculture, Nature and Food Quality.

*8 Official Food Control Authority of the Canton of Zurich, Chemical and Veterinarian State Laboratory of Baden -Württemberg, Institute for Food Investigation of the State Vorarlberg, State

La boratory of Basel-City, Kantonales Amt für Lebensmittelkontrolle, St Gallen.

*9 La boratoire National d’Essais Centre Logistique et Emballage at the request of Ansell Healthcare Europe N.V

n .a.Not analysed

n .i. Not indicated by the data source

DEP, DIPP and DMEP


DINP and DIDP, and the few reviews available mostly cite relatively old information and with little

information about use and alternatives. The information given here is therefore not restricted to the

EU.

ECPI has been asked for information on uses, consumption and alternatives in the European

context, but apart from the information cited below, it was not possible for ECPI to supply

information on these substances ECPI (2013e).

DEP


among others.

According to (NIEHS, 2006, USA): "DEP is used as a plasticizer in consumer products, including

plastic packaging films, cosmetic formulations, and toiletries, and in medical treatment tubing

(IPCS, 2003). It is used in various cosmetic and personal care products (e.g., hair sprays, nail

polishes, and perfumes), primarily as a solvent and vehicle for fragrances and other cosmetic

ingredients and as an alcohol denaturant (Labunska and Santillo, 2004). Other applications

include as a camphor substitute, plasticizer in solid rocket propellants, wetting agent, dye

application agent, diluent in polysulfide dental impression, and surface lubricant in food and

pharmaceutical packaging (ATSDR, 1995)."

FDA (2013, USA) states that: “The principal phthalates used in cosmetic products are

dibutylphthalate (DBP), dimethylphthalate (DMP), and diethylphthalate (DEP). They are used

primarily at concentrations of less than 10% as plasticizers in products such as nail polishes (to

reduce cracking by making them less brittle) and hair sprays (to help avoid stiffness by allowing

them to form a flexible film on the hair) and as solvents and perfume fixatives in various other

products. ”

DEP has been marketed by BASF (2008), as Palatinol® A (R), an additive with low odour for the

fragrances and cosmetic industries. According to BASF, DEP is soluble in the usual organic solvents

and is miscible and compatible with all of the monomeric plasticizers commonly used in PVC. DEP

was registered at ECHA under the commercial name Palatinol® A (R). This name was however not

found at BASF’s current product sites, and BASF is not among the registering companies, so they

may have abandoned the product by now, or transferred it to others. Polynt (2010), one of the

registrants, markets DEP for the following uses: Cellulose, flavours & fragrances, cosmetics,

pharma.

An anonymous source indicates current DEP use as plasticiser in EU. ECPI (2013e) does not have

information of its use as a plasticiser.

The German Bayrishes Landesamt für Gesundheit und Lebensmittelsicherheit (the Bavarian Health

and Food Authority; 2012) stated that DEP was allow ed for denaturing of alcohol in Germany, and

they found DEP in most of the analysed products in a survey of aftershaves, perfumes and eau de

toilette. These products were selected as having most relevance due to their high alcohol contents,

y et the survey does describe that DEP in cosmetics and personal care products can be used as a

fragrance carrier and plasticiser also. Their results are shown in Table 26.

As described further in Section 3 .3.2, DEP is as of 1 July 2013 not anymore among the accepted

substances for denaturing of alcohol in the EU (substances that are required in alcohol in order to

get exemption from alcohol tax).


TABLE 26

DEP CON CEN TRATION S FOUND IN TWO SURVEYS OF AFTERSHAVES, PERFUMES AN D EAU DE TOILETTE ON THE

GERMAN MARKET (BAYRISHES LAN DESAMT FÜR GESUNDHEIT U ND LEBEN SMITTELSICHERHEIT, 201 2).

DEP con centration ra nge

(%)

T est series in 2003; nu m ber of

sa m ples (% of sa m ples)

T est series in 2006; nu m ber of

sa m ples (% of sa m ples)

0 – 0,1 3 (= 12) 6 (= 23)

0,1 – 0,5 13 (= 52) 1 4 (= 54)

0,5 – 1,0 8 (= 32) 4 (= 15)

1,0 – 5,0 1 (= 4) 2 (= 8)

> 5,0 0 (= 0) 0 (= 0)

As regards nail polishes, DEP acts as a plasticiser to reduce cracking of the polish and as a film aid,

probably by keeping the polish floating until a clear film has been established and thereafter

partially evaporating from the surface (a principle used in PVC flooring with a resilient surface film,

not with DEP however). DBP seems to have been the most used plasticiser for nail polishes, but

DEP has been observed in some cases (US FDA, 2013). On the other hand, a survey of 23 nail

polishes/lacquers marketed in California in 2012 (focusing on DBP, toluene and formaldehyde),

found no DEP with the analysis methods used, but found DBP in 9 products (of which 7 with other

plasticisers as well) and no DBP but other plasticisers in other 9 products. In 5 products, no

plasticisers were observed with the used analytical methods. The other plasticisers observed were

camphor (mentioned as a secondary plasticiser as well as a fragrance), dioctyl adipate, tributyl

phosphate, butyl citrate, triphenyl phosphate, N-ethyl-o-toluene sulfonamide, N-ethyl-p-toluene

sulphonamide, P-toluene sulphonamide (tosylamide). Several of the product samples claimed to be

without DBP, but newer the less contained DBP in substantial concentrations (California EPA,

2012).

Similar information has not been found for the EU.

DIPP

According to the DIPP SVHC dossier (Environment Agency Austria, no year):"DIPP has been

registered for its use in the manufacture of propellants. As other low molecular weight phthalates

of carbon backbone lengths of C4 – C6 DIPP may also be used as plasticiser for PVC products and

other polymers due to their similar structure and physicochemical properties. Di-n-butyl

phthalate (DBP) and diisobutyl phthalate (DIBP) (linear and branched C4 esters) are used in

many PVC formulations, principally for ease of gelation. Owing to their relatively high volatility,

in comparison with other phthalates, they are often used in conjunction with higher molecular

mass esters. Diisopentyl phthalate (DIPP) is generally used in a similar manner (Ullmann, 2012).

However there is currently no registration for that use."

According to the REACH registration of the substance, it is registered by EURENCO Bofors AB, SE,

a company which produces explosives as well as charges - so-called propellants - for ammunition

(http://www.eurenco.com/en/propellants/index.html).

According to ECPI (2013e), DIPP is not produced in Europe anymore.

DMEP

DMEP is a specialty plasticiser which can be used in a number of polymers. According to BAuA

(2011): "The general global applications of DMEP have included its use as a plasticiser in the

production of nitrocellulose, acetyl cellulose, polyvinyl acetate (PVA, eds.) , polyvinyl chloride

Survey of selected phthalates 67

(PVC, eds.) and polyvinylidene chloride intended for contact with food or drink. DMEP is giving

these polymeric materials good light resistance. Further, it is used as a solvent. DMEP can

improve the durability and toughness of cellulose acetate (e.g. in laminated documents (Ormsby,

2005)) and can be used in “enamelled wire, film, high-strength varnish and adhesive. I t can also

be used in pesticide products internationally” (Canadian Screening Assessment, 2009).

Only limited information regarding DMEP in consumer products in the European marketplace

has been identified. The Danish Product Register records DMEP as a plasticiser in the

concentration range 0.1–1% in a material used to cover floors. The Swiss Product Register records

five consumer products with 1–5 % DMEP. One consumer product is a leather care product e.g.

for shoes, the other four consumer products are categorised as “paints, lacquers and varnishes”.

The information comes from older records and there are no current registrations of DMEP used in

consumer products (personal communication). Baumann et al. (1999) described the application of

DMEP as an additive for printer inks (“Kodaflex DMEP”). Cellulose acetate lamination films

typically contain 20–30% plasticisers by weight. DMEP and other phthalates are commonly

found in laminated documents (Ormsby, 2005). The Australian NICNAS (2008) has reported

about the import of DMEP in balls for playing and exercise, hoppers and children’s toys (e. g. as

inflatable water products) (Australian NICNAS, 2008).

There is no information whether the substance is still in use in articles on the EU market. "

According to CPSC (2011): “DMEP is used as a plasticizer for cellulosic resins, some vinyl ester

resins, PVC, and as a solvent, a molding component, and in adhesives, laminating cements, and

flash bulb lacquers. In I taly, dimethoxyethyl phthalate is permitted for use with food. U. S.

production of DMEP was estimated to be greater than 5000 pounds in 1977 and 1979 (HSDB

2010). The U.S. EPA’s Inventory Update Report (IUR) lists U.S. production/importation volume of

DMEP to be between 500,000 and 1,000,000 pounds in 1986, and 10,000 to 500,000 pounds in

the surveys conducted every four years from 1990–1998 (U.S. EPA 2002). After 1998, DMEP

production was no longer tracked by IUR.”

According to ECPI (2013), DMEP is not used as a plasticiser and the only European producer

stopped making this substance a few years ago.

3.3.2 Use in Denmark

The latest available aggregate survey of annual phthalate consumption in Denmark covers 2005-

2007 and is based on the revenues from the Danish environmental tax on phthalates (Brandt and

Hansen, 2009), in combination with other data on the application of phthalates. The situation may

likely be the same today, except that the assessment of which phthalates are used may be slightly

different today, as DINP is expected to be the main general plasticiser, while DIDP and DPHP are

primarily expected to be used in applications where resistance to heat or sunlight is prioritised (wire

and cable, roofing, tarps, etc.). DEHP may however still be present in a number of articles,

especially in import from Asia.


TABLE 27

ESTIMATED AN N UAL PHTHALATE CON SUMPTION IN 2005-2007 BASED ON THE REVENUES FROM THE DANISH

EN VIRON MEN TAL TAX ON PHTHALATES (BRANDT AND HANSEN , 2009)

Product group Used phthalates

(a ssessment by

Brandt and

Ha nsen, 2009)

Con su m pt ion of ph t h a la t es, t /y New rem a rks

Ca lcu la t ed from

income from tax on

ph thalates in 2005-

2007

Est imates share of

DEHP, DBP a nd

BBP

Wire and cable DIDP, DINP, DEHP 1 900 3 00-1200 DIDP likely dominate today;

DINP, DPHP, DEHP and PVC-

a n d-phthalate-free insulation

a lso used

T ube and hoses DINP, DEHP 6 30 7 0-140

Gloves, rainwear,

et c.

DINP, DIDP, DEHP 5 40 27 0-430

Roof plates DINP/DIDP, DEHP 1 60 <16

Film, sheets, tape DEHP, DINP 1 20 6 0-100

Ring binders and

document

pockets

(“stationary”)

DINP, DEHP 8 5 <17 PV C-free binders and pockets

dominate the market today

T arpaulins DINP, DIDP, DIOP

(DEHP)

2 8 <3 DEHP may have higher share in

th is product category

T a ble cloths,

cu rtains, etc.

DEHP (DINP) 9 5 -7

Coa ted steel

gu tters

DINP, DIDP, DEHP? 2 0,2-1

T otals 3 844 7 05-2014

Data from the Danish Product Register

Data on selected phthalates registered in the Danish Product Register were retrieved in June 2013

on the basis of the list of selected phthalates. The Danish Product Register includes substances and

mixtures for professional use which contain at least one substance classified as dangerous in a

concentration of at least 0.1% to 1 % (depending on the classification of the substance). Of the

selected phthalates, only DIPP and DMEP are classified as dangerous. For the other non -classified

substances, the registration will only occur if they are constituents of mixtures which are classified

and labelled as dangerous due to the presence of other constituents. The data consequently do not

prov ide a complete picture of the presence of the substances in mixtures placed on the Danish

market. On the other hand, for substances included in mixtures used for formulation of other

mixtures in Denmark (e.g. those included in raw materials used for production of paint), the

quantities may be double-counted as both the raw material and the final m ixture in the register. As

stated above, the amounts registered are for occupational use only, but for substances used for the

manufacture of mixtures in Denmark the data may still indicate the quantities of the substances in

the finished products placed on the market both for professional and consumer applications.

As shown in Table 28, DINP is clearly the major phthalate in professional products marketed in

Denmark, while the registered consumption of DIDP is moderate and the consumption of the other

phthalates is minimal, as expected. DIPP is not registered in the Product Register. It is expected

Survey of selected phthalates 6 9

that most of this import is used in Danish production, of which some is marketed domestically and

some is exported. DEP is seen to be used in 1 13 products across 49 companies, with non-

agricultural pesticides and preservatives as the major citable use (larger uses exist but may not be

cited). DMEP is only registered by a few companies.

The Product Register does not include non-chemical articles such as wire and cable, shoe-soles,

clothing, toys, etc., which likely constitute major parts of the Danish consumption of phthalates.

As shown in


Table 29, the major registered uses which can be mentioned with respect for confidentiality are adhesives and binding agents, fillers, paints, lacquers and varnishes. As noted, some other major applications across most substances cannot be mentioned due to confidentiality.

TABLE 28

SELECTED PHTHALATES – PU RE AND IN MIXTURES PLACED ON THE DANISH MARKET IN 2011 AS REGISTERED IN

THE DAN ISH PRODUCT REGISTER

CA S No Sh ort

na m e

Ch em ica l na m e Prod/Com

*2

Registered tonnage, t/y

Im port *1 Export Con sumption

84-66-2 DEP Diethyl phthalate 113/49 13 2 ,2 11

117-82-8 DMEP Bis(2-methoxyethyl) phthalate 3 /3 0-82 0-12 0-7 0

53306-54-0 DPHP Bis(2-propylheptyl) phthalate 1 8/5 1 0 1

26761-40-0 DIDP-1 1 ,2-Benzenedicarboxylic acid, di-

C9 -11-

1 4/11 8 1 7

68515-49-1 DIDP-2 br anched alkyl esters, C10-rich

Di-''isodecyl'' phthalate

4 4/15 4 23 37 5 4 8

DIDP total 5 8/26 4 31 37 6 55

28553-12-0 DINP-2 1 ,2-Benzenedicarboxylic acid, di-

C8 -10-

6 8/34 6 82 37 8 3 04

68515-48-0 DINP-1 br anched alkyl esters, C9-rich

Di-''ison onyl'' phthalate

2 5/8 7 6 2 7 4

DINP total 9 3/42 7 58 3 80 37 8

*1 : There is no phthalates production in Denmark.

*2 : Number of products /number of companies registered for substance.


TABLE 29

APPLICATION OF SELECTED PHTHALATES REGISTERED IN THE DANISH PRODUCT REGISTER, 201 2

CA S No Na m e Fu nct ion Con sumption (produ ct ion + im port –

export )

Fu nction code Number of

produ ct s

t /y

84-66-2 DEP*1 A bsorbents and adsorbents 01 6 0 .0046

Cleaning/washing agents 09 3 5 0.0171

Cosmetics 15 6 0 .0041

Im pregnation materials 31 4 0 .0001

Odour agents 3 6 2 6 0.0096

Non -agricultural pesticides and preservatives 3 9 1 2 0.4228

Pa ints, lacquers and varnishes 5 9 4 0 .0002

Surface treatment 6 1 8 0 .0002

117-82-8 DMEP *2 *2

26761-40-0 DIDP- 2 Fillers 2 0 4 5 .9781

28553-12-0 DINP-2 *1 A dhesives, binding agents 02 2 0 5 .5739

Fillers 2 0 27 2 1 .7020

Pa ints, laquers and varnishes 5 9 9 0 .0861

53306-54-0 DHPH *2 *2

68515-48-0 DINP-1 *2 *2

68515-49-1 DIDP-2 A dhesives, binding agents 02 2 1 8 .6736

Fillers 2 0 15 3 8.5337

*1 : The dominant uses cannot be reported due to confidentiality.

*2 : The uses cannot be reported due to confidentiality.

DEP in articles and mixtures

As regards cosmetics, personal care products and cleaning agents, The Danish Association of

Danish Cosmetics, Toiletries, Soap and Detergent Industries (SPT, 2013), informed that DEP has

three possible applications in their sector: Denaturing of alcohol used in articles and mixtures, as a

component in some fragrances and as film-forming substance in polymers used in nail polish. They

did not have specific information on whether there was any actual use in their sector for these

purposes in Denmark.

As mentioned above, DEP has been reported used for denaturing of alcohol. The aim of denaturing

is to make the alcohol unacceptable for consumption (alcohol for consumption is subject to national

tax).For attaining tax exemption for “fully denatured” alcohol in Denmark, alcohol produced or

used after 1 July 2013 shall be produced according to a specific formula containing 3 l

isopropy lalcohol (IPA), 3 l methylethylketon (MEK) and 1 gram denatoniumbenzorate per 100 litre

absolute alcohol. Alcohol being denatured by the previously demanded for mula and being bought

before 1 July 2013 may be marketed until the end of 2013 (Skat, 2013); i.e. not any contents of DEP.

Allowed denaturants for alcohol vary between EU countries, but according to the current rule,

denaturants allowed in one EU country are accepted in imports to other EU countries (SPT, 2013).


As per EU Regulation 162/2013 of 2 1 February 20131, a unified rule (with exemptions) was made

that the denaturing formula mentioned above should apply in EU countries for which nothing else

is mentioned in the regulation. A number of specified Member States have exemptions to the rule,

allowing other specified formulas for denaturing alcohols, but in none of the EU countries DEP is

on the list of accepted denaturants according to the regulation. The regulation also includes a list of

denaturing products accepted in the EU (across all Member States). The list does not include DEP.

The regulation entered into force 1 July 2013. The previous regulation on the issue (Regulation (EC)

No 3199/93) had a different scope but did also not mention DEP. Based on this information, it must

be expected that any denatured alcohol produced in the EU and marketed on its own or in articles

or mixtures after 1 January 2014 must be DEP-free. In other words, import of articles/mixtures to

Denmark from EU countries must be expected to be DEP-free, at least as of 1 January 2014. It has

not been investigated if DEP is currently accepted as a denaturing substance in non -EU countries,

and DEP could perhaps thus be a component in extra-EU import of cosmetics, etc.

Jørgen Gade Hyldgaard (2013), who is a consultant for more than half of the Danish producers of

cosmetics and personal care products on product safety issues, does not know of any Danish

producers using DEP. Contact to a major Danish producer of cosmetics confirmed this statement as

regards their own production. According to Hyldgaard, the function of DEP in fragrances is to delay

the ev aporation of the fragrance from the article/mixture.

While data on the consumption of DEP in articles have not been found, DEP has been included in a

number of analyses of consumer products performed as part of the Danish EPA's surveys of

chemicals in consumer products on the Danish market (as well as in other reports published by the

Danish EPA).

DEP was found in one of 20 toothbrushes at a quantity of 3 .1 µg/toothbrush (Svendsen et al.,

2004). Similarly, DEP was found in two out of 60 plastic sandals analysed by Tønning et al. (2010);

foam clogs and flip-flops, no concentration data were given. Tønning et al. (2008) found DEP in a

printed badge in a baby carrier at concentration of 60 and 350 µg/g, respectively, in two different

samples from the same product. In total, 13 baby products in the following product types were

analysed for phthalate content: Pillows for baby feeding, baby carriers, nursing pillows/ cushions

with different covers and stuffing, baby mattresses with stuffing of foam for beds, aprons for

perambulators, disposable foam wash cloths. Borling et al. (2006) found DEP at 1.5 mg/kg (or 1.5

µg/g) in an activity carpet and <3 mg/kg in a ball; for the other 6 products analysed, the

concentration was below <0.5 mg/kg. Nilsson et al. (2006) found DEP in the concentration 0.12

g/kg in one out of 1 5 sex toys analysed; a fetish glove of latex rubber. Tønning et al. (2009) found

DEP in PVC soap packaging, but DEP concentrations were not measured.

Further, Larsen et al. (2000) reports that DEP was found in concentrations up to 2.3 mg/kg in

textiles.

The relatively low concentrations indicate that DEP may either have been present as an impurity in

the plasticiser used or as a specialty plasticiser, or an auxiliary process substance with another

purpose, which function at low concentrations. While ECPI (2013e) has the understanding that DEP

is not used as a plasticiser, an anonymous data source indicates that it is used as such.

Data request from Danish trade and industry associations

The following Danish trade and industry associations have been contacted for data on the

phthalates covered in this survey:

Fugebranchen (the sealants suppliers’ and appliers’ organisation)

1 Regul ation 1 62/2013 of 21 February 201 3 amending the Annex to Regulation (EC) N o 31 99/93 on the mutual recognition of

pr ocedures for the complete denaturing of alcohol for the purposes of exemption f rom excise duty


DFL (Danish paints and glues industry)

The PVC Information Council Denmark

The Danish Plastics Federation

The Association of Danish Cosmetics, Toiletries, Soap and Detergent Industries

The Association of Danish Cosmetics, Toiletries, Soap and Detergent Indu stries provided general

information about the use of DEP in their sector (as cited above) and forwarded the data request to

their members, from which no replies were received as of the closure of the editing of this report . A

few of their members were contacted directly by COWI. DFL (2013) has informed that members

who responded to their inquiry in connection with this project did not use phthalates on the List of

undesirable substances (LOUS). Some did however report use of DIDP, in antifouling paints in

concentrations of 1 -6% and in a flexible adhesive, where it is part of an imported ingredient.

Fugebranchen (the sealants supplier and applier organisation) responded with specific information

about Danish conditions (information about one Danish producer using some of these phthalates).

The PVC Information Council Denmark (a part of The Danish Plastics Federation) kindly forwarded

our request for data to ECPI, which provided remarks on their understanding of the use of the

phthalates in question (as cited in relevant sections) and general data on consumption trends for

primary plasticisers (DINP, DIDP and DPHP).

3.4 Historical trends in use

Ov erall data on the trend in the use of phthalates are available from the web site of ECPI. ECPI

distinguishes between High Molecular Weight (HMW) phthalates with 7-13 carbon atoms in their

chemical backbone (with an average of C9-C10) and Low Molecular Weight (LMW) phthalates

(ECPI, 2013a) with less. According to ECPI, the most common types of HMW include DINP, DIDP,

DPHP, DIUP, and DTDP. DINP, DIDP and DPHP account for nearly 100% of the HMW. As shown

in the figure below, the consumption of the HMW (mainly DINP, DIDP and DPHP), has increased

from representing less than 25% of total phthalate sales in Western Europe in 1982,via about 50%

in 2001 to approximately 83% of the total sales in 2011 (ECPI, 2013a).

FIGURE 2

W ESTERN EU ROPE CONSUMPTION OF PHTHALATE PLASTICISERS (ECPI, 201 3A)

It is not specifically indicated how much of the high molecular weight phthalates referred to in the

figure above is represented by the different phthalates.

The total consumption of plasticisers, including phthalates, has been steady to slightly declining

within the EU during the last 10 years, driven by the increasing manufacture of PVC articles outside

the EU (as cited by COWI et al.,2012). While on a global scale producers still foresee an increase in

total manufacture and consumption of plasticisers, consumption within the EU is likely to continue

to be steady to slightly declining


A survey of Brandt and Hansen (2009) of phthalates in articles placed on the market in Denmark in

a historical perspective concludes in accordance with the general pattern in the EU that the

classified phthalates DEHP, BBP and DBP to a large extent have been replaced by the non-classified

phthalates such as DINP and DIDP.

DEP is reported to have been used in a large variety of consumer products. No information has

however been found about quantities used by application.


Phthalates are not produced in Denmark, but the EU is a major producer and exporter of ( ortho-)

phthalates.

DINP is produced by four companies within the EU in Germany, Belg ium and Italy , and is

registered in the 100,000-1,000,000 tonnes/y band. DIDP is produced by two companies within

the EU in Belgium and Italy, and is registered in the 100,000-1,000,000 tonnes/y band. DPHP

DPHP is produced in Germany and Sweden, and also registered in the 100,000-1,000,000

tonnes/y band.

DIPP is registered by one company in the 100-1000 tonnes/y band (a producer of explosives), and

is not produced in the EU anymore. DEP is registered by 5 companies in the 1000-10,000 tonnes/y

band; among the companies is one of the major manufacturers of phthalates. DMEP is not

registered under REACH and is reported to not be produced in Europe anymore.

The breakdown of the plasticiser market in Western Europe, USA and Asia can be

summarised as follows: DINP/DIDP represented 63% of the plasticiser market in Western Europe

in 2010, whereas it only represented 33% of the market in the USA and 21% of the market in Asia.

The total global market for plasticisers was estimated at 6 million tonnes, with 1.4 million tonnes in

Europe, the Middle East and Africa, 1.1 million tonnes in the Americas and 3 .5 million tonnes in

Asia (Calvin, 2011). Of the global plasticiser market, phthalates represented 84% (Calvin, 2011). The

on-going substitution of the traditional main general plasticiser DEHP has not reached the same

lev el in Asia as in Europe and the USA. Also, non -phthlate plasticiser and “linears/other phthalates”

are used to a higher extent in the USA than in Europe.

Danish net import in 2012 of phthalates on their own was still dominated by DEHP (C8; net

import around 800-1000 tonnes /y), but with the general C9-C10 plasticisers types including DINP

and DIDP/DPHP (net imports around 600-800 tonnes/y) as a major follow-up. The other three

plasticisers covered in this study are recorded with other phthalates in the trade statistics and the

group is traded in much lower numbers (net import around 90 tonnes/y).

The total plasticiser content of both imported and exported articles into and out of the EU has

been estimated at about 170,000 t/y. For the estimate of import/export of DINP/DIDP in articles it

was be assumed that DINP/DIDP accounted for the following percentages of the total plasticiser

consumption by region: EU, Switzerland, Norway, Iceland: 63%; the Americas: 33%; Asia and rest

of the world: 21%. Using these numbers, the import and export was estimated at 45,000 tonnes and

1 05,000 tonnes respectively, and the export corresponds to about 15% of the total use for

manufacturing of products with plasticisers in the EU. Correcting for a few article types not covered

in these estimates, the import of DINP/DIDP (should likely be considered as including the third key

general plasticiser DPHP) in articles was be estimated at approximately 50,000 tonnes and the

export at 125,000 tonnes. Of the import into the EU, 51% of the tonnage of the articles originates

from China, whereas only 9% of the imported DINP/DIDP (as such) is estimated to originate from

China. An overview of the extra-EU import/export by article type is shown in Table 23.


As regards the use in the EU, DINP, DIDP and DPHP have ov er the last decade taken over as

primary plasticiser for a major part of the former applications of DEHP. A s a consequence of the

different properties of the three substances, some differences in the use by application are seen.

DINP, DIDP and DPHP are typically used as primary plasticisers in PVC, sometimes in

combination with other plasticisers. The actual concentrations are quite variable and depend on the

desired properties of the final PVC. Actual analyses of plasticisers in different products demonstrate

that, for the same product, often different combinations of plasticisers are found. The combination

of plasticisers in a PVC material is partly governed by the desired performance characteristics of the


materials. Typical concentrations of DIDP in flexible PVC applications are reported to be around

25-50%, and the same seems to be the case for DINP.

DINP – DINP is a general plasticiser, which is applied in many products as the direct alternative

for DEHP, the formerly major general PVC plasticiser. As such DINP has a high consumption and is

probably the plasticiser which can be found in most flexible PVC products today. DINP has a wide

range of indoor and outdoor applications. DINP is a commonly used plasticiser, 95% of which is

used for flexible PVC used for construction and industrial applications, and durable goods (wire and

cable, film and sheet, flooring, hoses and tubing, footwear, toys, etc.). More than half of the DINP

used in non-PVC applications involves polymer-related uses (e.g. rubbers). The remaining DINP is

used in inks and pigments, adhesives, sealants, paints and lacquers (where it also acts as a

plasticiser) and lubricants (ECPI, 2013b).

DIDP - DIDP is a common phthalate plasticiser, used primarily to soften PVC. DIDP has properties

of v olatility resistance, heat stability and electric insulation and is typically used as a plasticiser for

heat-resistant electrical cords, leather for car interiors, and PVC flooring. (ECPI, 2013c). Non-PVC

applications are relatively small, but include use in anti-corrosion and anti-fouling paints, sealing

compounds and textile inks.

DPHP - DPHP is often used as an alternative (to DIDP) because only minor compound changes are

needed to adapt wire formulations for example to DPHP (ECPI, 2013d). It is used automotive and

outdoor applications (roofing, geo-membranes, tarpaulins, etc). Almost all DPHP is used as a

plasticiser to make PVC soft and flexible.

A total breakdown of the consumption by application in the EU of the three phthalates by is not

av ailable. COWI et al. (2012) produced a best available scenario for the breakdown of the

consumption by 2015 based on the available data from industry. The major article types were wires

and cables, film and sheet, flooring, and various other coated products.

DEP, DIPP and DMEP


DINP and DIDP, and the few reviews available are mostly relatively old and with little information

about use and alternatives.

DEP


among others. DEP is reported to be have been used as a plasticizer in consumer products,

including plastic packaging films, cosmetic formulations, and toiletries, and in medic al treatment

tubing. Also in various cosmetic and personal care products (e.g., hair sprays, nail pol ishes, and

perfumes), primarily as a solvent and vehicle for fragrances and other cosmetic ingredients and as

an alcohol denaturant. DEP is however not mentioned as an accepted denaturant in EU and Danish

rules from 2013 on tax exemption for denatured alcohol (exemption requires use of specified

denaturants). An anonymous source indicates current DEP use as plasticiser in EU. ECPI does not


have information of its use as a plasticiser. Other applications include as a camphor substitute,

plasticizer in solid rocket propellants, wetting agent, dye application agent, diluent in polysulfide

dental impression, and surface lubricant in food and pharmaceutical packaging, in preparation of

pesticides. Polynt, one of the registrants, markets DEP for the following uses: Cellulose, flavours &

fragrances, cosmetics, pharma.

DIPP

According to the registration of the substance, it is registered by EURENCO Bofors AB, SE, a

company which produces explosives as well as charges - so-called propellants - for ammunition.

DIPP may also be used as plasticiser for PVC products and other polymers due to their similar

structure and physicochemical properties, but this use is not registered.

DMEP

DMEP is a specialty plasticiser which can be used in a number of polymers. The general global

applications of DMEP have included its use as a plasticiser in the production of nitrocellulose, acetyl

cellulose, PVA , PVC and polyvinylidene chloride intended for contact with food or drink. DMEP is

giv ing these polymeric materials good light resistance. Further, it is used as a solv ent. Only limited

information regarding DMEP in consumer products in the European marketplace has been

identified. There is no information whether the substance is still in use in articles on the EU market.

As mentioned, DMEP is not registered under REACH.

The latest available aggregate survey of annual phthalate consumption for Denmark covers

2005-2007 and is based on the revenues from the Danish environmental tax on phthalates, in

combination with other data on the application of phthalates. The major article groups as regards

phthalate consumption were wires and cables (1900 tonnes/y), tubes and hoses (630 t/y), and

glov es and rainwear (540 t/y). The situation depicted may likely be the same today, except that the

assessment given of phthalates used may be slightly different today, as DINP is expected to be the

main general plasticiser, while DIDP and DPHP are primarily expected to be used in applications

where resistance to heat or sunlight is prioritised (wire and cable, roofing, tarps, etc.). DEHP is

however likely still present in a number of articles.

Data on selected phthalates registered in the Danish Product Register were retrieved in June

2013 on the basis of the list of selected phthalates. The Danish Product Register includes substances

and mixtures for professional use which contain at least one substance classified as dangerous in a

concentration of at least 0.1% to 1 % (depending on the classification of the substance). Of the

selected phthalates, only DIPP and DMEP are classified as dangerous. DINP is clearly the major

registered phthalate in professional products marketed in Denmark, while the registered

consumption of DIDP is moderate and the consumption of the other phthalates is minimal, as

expected. DIPP is not registered in the Product Register. The Product Register does not include

non-chemical articles such as wire and cable, shoe-soles, clothing, toys, etc., which constitute major

parts of the Danish consumption of phthalates. Major registered uses which can be mentioned with

respect for confidentiality are adhesives and binding agents, fillers (likely to be understood as

including sealants), paints, lacquers and varnishes. Some other dominant applications across most

substances cannot be mentioned due to confidentiality.

Data gaps

More specific information on the consumption of DINP, DIDP, DPHP and DEP by application.


4. Waste management

4.1 Waste from m anufacture and use of selected phthalates

For plasticiser uses of the covered phthalates, the releases to waste from production (formulation

and conversion) are not well described according to COWI et al. (2009). Releases to waste are



produced.

For paints and sealants, the “conversion” is defined as the occasion when the material is applied,

ty pically at a construction site or in manufacturing of machines or other large articles. The use in

construction sites is expected to potentially produce more waste as leftovers in seal ants tubes, and

in paint crates, because the need for materials is less well defined.

For all articles, the major release with waste is expected to take place with the end product at the

stage of its disposal; this is dealt with below.

4.2 Waste products from the use of selected phthalates in m ixtures and

articles

Table 27 in Section 3.3.2 on use in Denmark gives the best available overview of the major waste

fractions with contents of phthalates, as well as estimates of the amounts of phthalates in this waste.

As shown there, the phthalates-containing waste fractions with the major phthalate contents are

cable and wire, tube and hoses, gloves and rainwear, roof plates; film, sheets and tape.

The situation depicted is likely a good reflection of the current waste stream, and this picture is not

expected to change quickly. Flexible PVC seems to be a material which will keep its prevalence on

the market, and most manufacturers in the EU and globally still uses ortho-phthalates in the

production. There are indications that the share of non-ortho-phthalates in the flexible PVC market

has been rising gradually ov er the last decade or so, especially in sensitive applications such as toys,

PVC for food contact and some medical applications. This trend is expected to continue, probably at

a moderate pace, at least until the entering into force of the Danish general ban on certain

phthalates (in 2014/2015).

The amounts of flexible PVC in each article group subject to the Danish PVC and phthalates tax, are

roughly estimated in Table 30 based on the data presented by Brandt and Hansen (2009). Not all

product groups containing flexible PVC are covered, but the study is deemed to include most of the

flexible PVC consumption which is plasticised with phthalates. The uncertainty on the figures are

mainly due to the fact that many of the article types are not reported in specific commodity groups

in the trade statistics used, but rather in aggregated groups of different article types. The estimates

are based on assumptions of the share of flexible PVC in each relevant commodity group of the

statistics.

As regards non-PVC uses of the phthalates, they represent much smaller phthalate amounts and in

most cases occur in lower concentrations (deemed from Danish Product Register data and

knowledge about the use patterns.


TABLE 30

ROU GHLY ESTIMATED AN NUAL CON SU MPTION OF MAJOR ARTICLE GROPUS MADE W ITH FLEXIBLE PVC IN 2005-

2007 . BASED ON DATA FROM (BRAN DT AND HANSEN , 2009)

Product group Con su m pt ion , t /y A ssumed sh a re of

flexible PV C in

commodity code *1 A ll m a t eria ls in

cu st om codes

inclu ded*1

Flexible PV C wit h

t h ese a rt icles

Wire and cable 3 7 ,000 9 ,300 0 .25

T u be a nd h oses 2 ,300 2 ,300 0 .3

Gloves, rainwear, etc. 1 ,600 2 00 0 .42

Flooring 4 ,100 4 ,100 0 .25

Roof plates 9 00 9 00 NA

Film, sheets, tape 1 ,700 3 00 0 .19

Ring binders and document

pockets (“stationary”) 5 ,300 3 00 0 .3

T arpaulins 4 00 1 00 0 .42

T a ble cloths, curtains, etc. 160 3 0 0 .42

Coa ted steel gutters NA NA NA

T otals (rounded) 5 3,000 1 8,000 -

Note: *1: Many commodity codes in the trade statistics include several article types, also such which are not

m ade with flexible PVC. Assumption was made on share of flexible PVC in articles reported under each code; see

Br andt and Hansen (2009) and their sources.

Phthalate concentrations in articles

The total concentrations of plasticisers in polymer articles becoming waste vary depending on the

flexibility of the article type; the more flexible, the higher plasticiser concentration (within each

poly mer type). This will particularly be reflected in the concentration of the main plasticiser in the

article, typically DINP, DEHP, DIDP, DPHP or similar high molecular weight plasticiser. Ranges

and averages of concentrations of the general plasticisers DINP and DIDP in articles are

summarised from available studies in Table 25 in Section 3 .3.1 on the use in EU. According to the

Danish Waste Order (Affaldsbekendtgørelsen - BEK 1 309 of 1 8. Dec. 2012), waste with more than

0.5% of substances which are classified as Repr. 1 B (reprotoxic, such as DIPP and DMEP) is

classified as hazardous waste

As for specialty plasticisers including DEP, DIPP and DMEP, if present, their concentration will

more likely vary with the processing conditions prevailing in the manufacturing of the article

(process temperature, speed, etc.), and as a consequence of price or other more incidental aspects

(many different phthalates and non-phthalate plasticisers may be used for the same purposes). The

few available examples of DEP concentrations in consumer products described in Section 3.3.2 are

summarised in Table 31 below. Note that these results often each represent very broad articles

groups, and that the rest of the articles analysed had DEP concentrations below the detection limits

in the studies. The data shown in the table can thus not be considered as representative for the

article type, but rather as an indication that DEP may occur in waste of these types. As shown,

except for the sex toy sample, DEP was found in trace concentrations only , and for such low

concentrations there is no certainty whether DEP has been added intentionally, or is a consequence

of impurities in the plasticisers used.


TABLE 31

SU MMARY OF DEP CON CEN TRATIONS FOUND IN SELECTED ARTICLE TYPES IN RECEN T STU DIES

A rticle type Number of

sa m ples

DEP

con centration *1,

m g/kg

Rem a rks

Ba by carrier 13 6 0 and 350 In two parts of the same sample, a

pr inted badge

A ctivity carpet for

ba bies

8 1 .5 in 1 sample

Ba ll for children 8 <3 Detection limit was 0.05

Sex t oys; fetish glove 15 1 20 In 1 sample

T extiles ? Up to 2.3 mg/kg

Pla stic sandals 6 0 ? DEP detected, but not measured,

in 2 samples

PV C soap packaging ? ? DEP detected, but not measured.

Note: *1: References for the data are shown in Section 3.3.2.

The Danish Waste Order (BEK nr 1309 of 1 8/12/2012) stipulates that PVC shall, to the extent

possible, be sorted out from the waste and be collected for recycling. PVC waste for which no

recycling schemes are available should be separated from waste intended for incineration and

landfilled. In Denmark, recycling schemes exist for hard PVC only (“Wuppi” and others), meaning

that flexible PVC shall be collected separately and deposited. Consumers generally have difficulties

in separating specific waste fractions, and as flexible PVC is part of many ordinary consumer

products like rainwear, boots, packaging, etc., for which the content of PVC is not obv ious to the

consumer, much consumer waste is deemed disposed to municipal waste to be incinerated.

Phthalates are oil derivatives which will most likely be destroyed in controlled waste incineration

plants under Danish conditions. The PVC polymer and other non -combustible additives however

produce a high amount of solid residues per weight unit of PVC waste incinerated. During

incineration PVC acts as a source of gaseous hydrochloric acid and may as such contribute to

corrosion of the boiler. Because of this the incineration plants would like to avoid excessive

amounts of PVC.

Industrial waste and other waste from professionals may likely have a higher separate collection

rates for flexible PVC waste. No documentation for this was found however.

4.3 Release of selected phthalates from waste disposal

In landfills, a part of the phthalates in polymers may slowly be washed out of the articles and will

(in Denmark) be lead with the leachate to municipal wast e water treatment plants. In waste water

treatment plants, much of the phthalate content will be adsorbed to particles and will be collected

with the sludge and used as fertilizer on agricultural land if certain thresholds for phthalate

concentrations and other specified environmental pollutants are met (see Section 2.1.1). If these

thresholds are not met the sludge is incinerated or in rare cases landfilled (< 1 %).

In the case of DEP, which is to a higher degree used in applications where they may be washed of

(cosmetics, personal care products, cleaning agents, etc.), a bigger part of the DEP present in the

articles and mixtures may be lead to waste water treatment.

EC (2003b) refers a Danish study from 1999 where the conten t of DINP in sewage sludge from a

few municipal WWTPs was measured and generally found to be in the range 1.5 – 6.7 m g/kg dw.

Prev iously, DINP and DEP were determined routinely in sewage sludge from Danish municipal


WWTPs as part of the point source programme under the national Danish environmental

monitoring programme, NOVANA. However, the newest NOVANA data that include sludge

analyses are from 2004 (Danish EPA, 2005a) where the average concentration of DINP was found

to be 1 6.8 mg/kg dw (a high concentration compared to e.g. 2003 where the average was 4.6 mg/kg

dw (Danish EPA, 2005a)) while DEP was found at an average concentration of 0.15 mg/kg dw (0.03

mg/kg in 2003). None of the other selected phthalates were included in the study.


For plasticiser uses of the covered phthalates, the releases to waste from production (formulation

and conversion) are not well described according to COWI et al. (2009). Releases to waste are



produced. For sealants, paints and non-polymer uses, the “conversion” situation includes

application on construction sites, etc. and here, a higher fraction of the material may be disposed as

waste due to the less well defined conditions

The amounts of flexible PVC in articles subject to the Danish PVC and phthalates tax, are roughly

estimated at 18,000 tonnes/year. Not all product groups containing flexible PVC are covered, but

the figure is deemed to include most of the flexible PVC consumption which is plasticised with

phthalates. The phthalates-containing waste fractions with biggest phthalates contents are cable

and wire, tube and hoses, gloves and rainwear, roof plates; film, sheets and tape. The situation

depicted is likely a good reflection of the current waste stream, and this picture is not expected to

change quickly, at least until a product life time after the entering into force of the Danish ban on

certain phthalates (in 2014/2015). The non-PVC uses of the phthalates represent much smaller

phthalate amounts and lower phthalate concentrations.

Ranges and averages of concentrations of the general plasticisers DINP and DIDP in articles are

summarised from available studies in Table 25 in Section 3 .3.1 on the phthalate use in EU.

As for specialty plasticisers including DEP, DIPP and DMEP, if present, their concentration will

more likely vary with the processing conditions prevailing in the manufacturing of the article

(process temperature, speed, etc.), and as a consequence of price or other more incidental aspects

(many different phthalates and non-phthalate plasticisers may be used for the same purposes).

Table 31 summarises the available measurements of DEP in consumer products; DEP has been

observ ed in a few samples of children’s articles, plastic sandals, PVC soap packaging and sex toys.

The Danish waste order stipulates that PVC shall, to the extent possible, be sorted out from the

waste and be collected for recycling. PVC waste for which no recycling schemes are available should

be separated from waste intended for incineration and deposited on controlled waste deposits. In

Denmark, recycling schemes exist for hard PVC only (“Wuppi” and others), meaning that flexible

PVC shall be collected separately and deposited. Consumers generally have difficulties in separating

specific waste fractions, and as flexible PVC is part of many ordinary consumer products like

rainwear, boots, packaging, etc., for which the content of PVC is not obv ious to the consumer, much

consumer waste is deemed disposed to municipal waste to be incinerated.

Data gaps

Inv estigation of the fate of plasticised PVC waste in Denmark, including recycling rates, for

both consumer waste and waste from professionals.


5. Environmental effects and exposure

Apart from the commercially most important phthalates, DEHP, DBP, BBP and DIBP, which have

been studied extensively and for which e.g. Annex XV restriction dossiers have been prepared, the

body of env ironmental information on most other phthalate esters is rather limited or even sparse.

This also includes the phthalates selected for this review with the exception of DINP and DIDP, for

which EU risk assessment reports have been prepared in 2003 (although not based on a very large

amount of environmental data), and to some extent DMEP for which a screening assessment report

has been prepared by Environment Canada (2009). This chapter is largely based on these reports

and, for the remaining substances, on registration information published by ECHA.

5.1 Environmental hazard

5.1.1 Classification

Only two of the substances covered by this review have agreed harmonised CLP classifications;

DIPP and DMEP (see section 2.1.2). Regarding environment only DIPP has an agreed classification,

namely Aquatic Acute 1 with the Hazard Statement Code H400.

A number of notifiers of the remaining substances have provided self-classifications that are

presented in full in section 2.1.2 and for which the proposed environmental classifications are

summarised in Table 32 below. For substances not mentioned in the table, no environmental

classification has been proposed. It should be noted that the vast majority of notifiers have not

prov ided any self-classification of the notified substances (see section 2.1.2).


TABLE 32

EN VIRON MEN TAL CLASSIFICATION INFORMATION ON NOTIFIED AND REGISTERED SU BSTAN CES RECEIVED FROM

MAN U FACTURERS AND IMPORTERS (C&L IN VEN TORY)

CA S No Su bst a nce na m e Ha zard Class and

Ca tegory Code(s)

Ha za rd

St a t em ent

Codes

Nu m ber of

not ifiers

68515-48-0 1 ,2-Benzenedicarboxylic



T otal

No. of environ.

classifications

A quatic Acute 1

H400

269

2 4

2 4

28553-12-0 Di-''ison onyl'' phthalate T otal

No. of environ.

classifications

A quatic Acute 1

A quatic Acute 1 +

A quatic Chronic 1

A quatic Chronic 4

H400

H400 + H410

H413

857

5 2

1

2 3

2 8

26761-40-0 Di-''isodecyl'' phthalate T otal

No. of environ.

classifications

A quatic Acute 1

A quatic Acute 1 +

A quatic Chronic 1

A quatic Chronic 2

H400

H400 + H410

H413

182

8 4

1 8

2 3

4 3

It is assumed that some of the discrepancies in the above self-classifications are due to differences

in the interpretation of toxicity results obtained at concentrations above the solubility limits of these

poorly water soluble substances.

5.1.2 Environmental effects

DIDP

The risk assessment reports for DIDP (EC, 2003a) refers five acute studies on four species of fish

(Onchorhynchus mykiss, Pimephales promelas, Lepomis macrochirus, Cyprinodon variegatus ) for

which no effects were observed at the maximum concentrations tested (0.47 to 1 mg/l). These

concentrations are all significantly above the solubility limit of the substance in water (0.038 µg/l)

and were therefore obtained by preparing emulsions of the test substance (some showing presence

of undissolved particles). Reliable studies at concentration s below the solubility limit are not

considered possible to carry out in practice. In the ECHA registration information, the study with O.

mykiss (LC50 ≥0.62 mg/l) is considered to be the key study. No studies on chronic effects on fish

exposed to DIDP v ia the water phase have been carried out and no significant effects were observed

when medaka (Oryzias latipes) was exposed in a two-generation study to 20 mg DIDP/kg feed for

284 days (EC, 2003a).

Based on the results of chronic fish studies with a number of C6 -C11 phthalates (e.g. DEHP, DOP

and DINP), EC (2003a) concludes that “based on the available data, DIDP has no adverse effects

upon fish” and “a NOEC cannot be determined”.

Similarly, the acute toxicity studies with invertebrates performed with daphnids ( Daphnia magna,

Mysidopsis bahia, Paratanytarsus parthenogenetica) at max. concentrations above the solubility

limit (0.15 to 500 mg/l) did not demonstrate any effects at the limit of solubility in water. A NOEC

of 0.03 mg/l in a 21 day study with D. magna was considered to be due to physical entrapment of


the test organisms rather than a toxic effect, and therefore EC (2003a) concludes that no chemical

toxic effects could be observed and, consequently, no NOEC could be derived.

Neither could toxic effects on sediment dwellers, algae or microorganisms be observed in the tests

performed (EC, 2003a).

Av ailable data indicate no effects of DIDP on soil dwelling or other terrestrial organisms (EC,

2003a). A PNEC for soils was determined at 100,000 µg/kg soil.

The potential of DIDP to cause endocrine disruption in the environment is discussed by EC (2003a)

based on the findings in the abovementioned feeding study with medaka (Oryzias latipes). As no

parameters and endpoints indicated any effects on eggs, embryos or fish, EC (2003a) concludes that

“there is apparently no impact on any population parameter from chronic exposure to DIDP on

fish”.

DINP

A risk assessment report very similar to the one for DIDP (and to a large extent based on the same

studies and references) was prepared for DINP (EC, 2003b). Acute toxicity tests on fish were

performed using the same four fish species as for DIDP (Onchorhynchus mykiss, Pimephales

promelas, Lepomis macrochirus, Cyprinodon variegatus ) and two more (Brachydanio rerio,

Leuciscus idus) at concentrations ranging from 0.16 to 500 mg/l compared to a solubility limit in

water of 0.6 µg/l. Based on the results obtained, EC (2003b) concludes that “no acute effects have

been reported in fish with DINP at its limit of solubility and above in the test system”.

In a chronic two-generation feeding study with medaka (Oryzias latipes) similar to the one

described for DIDP, a “slight but statistically significant increase in egg viability in the DINP treated

group when compared to the no treatment control” was observed, but no other effects. In total,

based on this study and the results of chronic fish studies with a number of C6-C11 phthalates (e.g.

DEHP, DOP and DINP), EC (2003b) concludes that “based on the available data, DINP has no

adv erse effects upon fish” and “a NOEC cannot be determined”.

Similar to DIDP, no effects on invertebrates, sediment dwellers, algae and mic roorganisms were

observ ed in the tests performed with DINP.

A PNEC for soils was determined at 30,000 µg/kg soil.

The potential of DINP to cause endocrine disruption in the environment is discussed by EC (2003b)

based on the findings in the abovementioned feeding study with medaka (Oryzias latipes). EC

(2003b) concludes that “there is apparently no impact on any population parameter from chronic

exposure to DIDP on fish”.

DMEP

DMEP is not registered by ECHA, which therefore has no data on the substance. However, a

screening assessment was carried out in 2009 by Environment Canada, which is the main source of

specific environmental information on this substance.

DMEP was tested experimentally for acute toxicity on 7 aquatic species representing three trophic

lev els: fish, invertebrates and molluscs. LC50 was higher than 117 mg/l (nominal) for all species

except Daphnia magna (crustacean) for which an LC50 = 56 mg/l was determined.

Env ironment Canada (2009) also lists results of QSAR modelling by different models of acute and

chronic toxicity of DMEP to fish, daphnia and algae of which the lowest acute LC50/EC50 value is


4 .3 mg/l for fish (range of all acute toxicities is 4.3 – 452 mg/l) while the lowest chronic NOEC is 14

mg/l, also for fish.

It is mentioned by Environment Canada (2009) that there is uncertainty about the actual value of

some central physical-chemical properties of DMEP such as Log Kow and water solubility and that

the model results therefore are associated with some uncertainty (a water solubility of 8,500 mg/l

and a Log Kow of 0.04 are used but there is also a reference to a reported water solubility of 900

mg/l and a Log Kow = 2.9).

DMEP was not toxic to rye grass and lettuce at concentrations of 1 17 mg/l. No other effect data on

terrestrial organisms are mentioned.

DEP

ECHA registration data for DEP comprises acute toxicity data on four species of fish of which the

lowest v alue is 12 mg/l for rainbow trout (values for other fish species range from 17 to 29 mg/l).

For daphnia the key study gives an EC50 = 90 mg/l while a supporting study gave an LC50 = 52

mg/l. The EC50 for algae was determined to be 23 mg/l in a 72 hour study.

The ECHA data do not comprise chronic data on fish or algae while the key study NOEC (21 days)

for daphnia did not show any effects at the highest test concentration of 25 mg/l.

DIPP

The only information about DIPP at the ECHA site is a short statement for invertebrates and algae

say ing that DIPP is predicted not to be toxic to aquatic invertebrates or algae.

DPHP

For DPHP an 96 hour, static test LC50 >10,000 mg/l for zebra fish is reported by ECHA while there

is data waiving for chronic data on fish. The acute (48 h) EC50 for daphnia is reported to be higher

than 100 mg/l as is the 72 hour toxicity to green algae.

A chronic (21 days) reproduction study on daphnia did not result in observations of any adverse

effects of DPHP at the highest test concentration of 1 mg/l.

5.2 Environmental fate

Env ironmentally relevant physic-chemical properties such as water solu bility and Log Kow differ

significantly between the phthalates selected for this study. Thus, the short-chain phthalates DEP

and DMEP have water solubilities close to 1 ,000 mg/l whereas the solubilities of DPHP, DIDP and

DINP are in the sub-µg/l range. Likewise, Log Kow’s range from 2-3 for DEP and DMEP to 8-1 0 for

DPHP, DIDP and DINP (see section 1.2).

Howev er, according to the public registration data found on ECHA’s web-site, all of the registered

phthalates in this study appear to be classifiable as “readily biodegradable” and therefore it is

considered likely that also the only non-registered substance, DMEP, is readily biodegradable

although firm documentation of this is lacking. Experimental data indicate that also in aerobic

sediment the biodegradation of DINP and DIDP takes place fast (DT50 values of 1 day or less) while

for the other substances there is no information on degradation in natural water and sediment (data

waiving). No data on degradation rates in soil are available.

Abiotic degradation/transformation in air takes place for DINP and DIDP with half-lives of about 5

hours, for DMEP with a half-life of 6.6 hours and for DPHP with a half-life of 1 4 hours (all results

based on modelling). Only DEP appears to have a longer half-life in air; 111 hours (modelled).

Photoly sis and hydrolysis appear not to be processes of any relevance for the dissipation of

phthalates in the environment.


Sorption to organic matter is strong for the long-chained phthalates, ECHA reports KOC v alues for

DIDP and DINP of 1 ,589,000 and 793,000-948,000, respectively, and >426,580 for DPHP.

Howev er, DEP has a KOC in the range 1 50-500 (medium mobility in soil).

Regarding bioconcentration/bioaccumulation potential the EU risk assessment report for DIDP

(EC, 2003a) mention an experimental BCF <14.4 for the fish (Cyprinus carpio), which, however,

the authors find is too low compared to other data e.g. on DEHP and therefore recommend the BCF

= 860 established for DEHP in fish to be used for risk assessment. A BCF = 4,000 for DIDP in

mussels is recommended for use in secondary poisoning risk assessment. For soil organisms a BCF

= 1 is recommended as a reasonable worst-case BCF. The same BCF v alues are used/recommended

for DINP (EC, 2003b).

None of the substances are considered to meet the criteria for being classified PBT or v PvB.

5.3 Environmental exposure

5.3.1 Sources of releases

None of the phthalates in this study are manufactured in Denmark and therefore such sources of

release are not relevant for this country. There are downstream users of some of the phthalates, in

particular DINP, for manufacturing of v arious polymers, which are considered point sources of

release to the atmosphere and to some extent also to wastewater.

General sources of release are outlets from waste water treatment plants (WWTPs) and separate

rain runoff sy stems as well as atmospheric deposition of substances emitted to air. A wet deposition

rate for DINP of 1 7 -33 µg/m2/year (1998) has been calculated for a background location in

Denmark based on analytical measurements (EC, 2003b). No newer data on the issue has been

identified.

As for DINP, measured data are not given by Boutrup and Svendsen (2012), but they refer to the so-

called “key number” (Danish: Nøgletal; defined as the 75% percentile of measurements in the

period 1 998-2009, (Kjølholt et al., 2011)) which is considered to be the best estimate of a national

mean value for calculation of total releases from WWTPs. For DINP releases from municipal waste

water plant outlets is 0,37 µg/l (interval 0.19-0.56). The similar key number for DEP is 0.33 µg/l

(0.20-0.63) .

TABLE 33

TREN DS IN CON CENTRATION S OF SELECTED PHTHALATES IN OUTLETS FROM MW W TP 2000-201 0 (BOU TRUP AND

SVEN DSEN , 201 2)

Year DEHP DEP DINP DBP

Mean

µg/L

95% ft

µg/L

%

a bov e

d.l .

Mea n

µg/L

95% ft

µg/L

%

a bove

d.l .

Mea n

µg/L

95% ft

µg/L

%

a bove

d.l .

Mea n

µg/L

95% ft

µg/L

%

a bov e

d.l .

2000 1 ,9 6 6 0 0,5 1 3 0 - - 2 0 ,8 1 ,5 2 2

2001 2 ,8 11 6 8 0,8 2 ,2 37 0,3 0,4 5 0,9 1 ,8 2 8

2002 3 13 6 4 0,4 0,7 4 0,7 2 ,9 7 0 ,3 0,4 6

2003 1 ,8 6 ,1 27 0,2 0,6 15 - - 0 ,5 0,1 0 ,4 7

2004 1 ,9 5 ,2 5 9 1 ,5 7 ,1 5 6 1 ,3 5 ,8 3 6 0,14 0,27 3 6

2010 0,5 - 6 5 - - 9 0 ,6 - 17 NA NA NA

Boutrup and Svendsen (2012) also estimated the total release of certain plasticisers, including DINP

and DEP, to Danish marine waters. The results are shown in Table 34, along with those for DEHP


for comparison. No sums were calculated by the authors, but as shown, DEP releases were

estimated as of the same order of magnitude as DINP from these numbers. Estimated releases of

both DINP and DEP are considerably smaller than that for DEHP, which might reflect that the used

concentration value for DINP may not adequately reflect the most recent consumption pattern,

where DINP is the main general plasticizer and the DEHP consumption has declined.

TABLE 34

ESTIMATED TOTAL RELEASES OF DIN P, DEP AN D DEHP FROM MU N ICIPAL W ASTE WATER TREATMEN T (BOU TRUP

AN D SVEN DSEN , 201 2).TERE

Year DINP DEP DEHP

Recipient Inpu t Int erv a l Inpu t Int erv a l In pu t Int erv a l

1 Nordsøen 5 ,9 3 ,1-9 5 ,3 3 ,2-10 4 5 2 3-96

2 Ska gerrak 1 ,4 0,7 -2,1 1 ,2 0,8-2,4 11 5 ,3-23

3 Ka ttegat 3 0 1 6-46 27 1 6-51 2 26 114-490

4 N. Bæ lt 6 ,1 3 ,1-9 5 ,4 3 ,3-10 4 6 2 3-99

5 Lillebælt 1 8 9 ,4-28 1 6 9 ,9-31 139 7 0-298

6 St orebælt 1 4 7 ,3-22 13 7 ,7-24 1 08 5 4-231

7 Øresund 57 2 9-86 51 31-97 4 31 2 16-924

8 S. Bælthav 0,5 0,2-0,7 0,4 0,2-0,8 3 ,5 1 ,7-7,5

9 Øst ersøen 3 ,1 1 ,6-4,7 2 ,8 1 ,7-5,3 2 4 1 2-51

Boutrup and Svendsen (2012) has estimated a total release of DINP from WWTP’s to the marine

areas surrounding Denmark of around 135 kg/year.

5.3.2 Monitoring data

Boutrup and Svendsen (2012) summarised observed concentrations of selected plasticisers

measured in municipal waste water treatment plant outlets. The data for DEHP and DINP as

representatives of general plasticisers, and DEP and DBP as representatives of specialty plasticisers

(and DEP as solv ent) are presented in Table 33. The reference also gives data for BBP and the non -

phthalate plasticiser DEHA (diethylhexyl adipate). The authors note that in general, the releases of

the measured plasticisers were lower in 2010 than in earlier years; they however consider the data

material to be too small to make clear statements as to whether this can be deemed as a decreasing

trend.

Only two of the phthalates, DEP and DINP, are included in the national Danish environmental monitoring programme, NOVANA, and only for releases from point sources such as WWTPs and separate outlets for rain runoff. Data from NOVANA on these substances area summarised in Table 35 below.


TABLE 35

MON ITORIN G DATA FOR SOME PHTHALATES IN OUTLETS FROM POINT SOURCES FROM THE NATIONAL DANISH

MON ITORIN G AND ASSESSMEN T PROGRAMME (N OVANA).

Su bstance Point source Number of

sa mples *1

A v era ge

µg/L

Median

µg/L

Yea r Sou rce

DEP WWTP 3 0 (10) 0.19 0.00 2 011 Da n ish Nature Agency, 2012

DEP WWTP 3 6 (20) 1 .52 - 2 004 Da n ish EPA, 2005b

DINP WWTP 3 0 (10) 1 .05 0.00 2 011 Da n ish Nature Agency, 2012

DINP WWTP 3 6 (13) 1 .26 - 2 004 Da n ish EPA, 2005b

DINP Ou tlets for

r a in runoff

- 0 .9 - 2 007-2009 Bou trup and Svendsen, 2012

*1 Number of positive samples in brackets

EC (2003b) refers for DINP some earlier investigations carried out in Denmark by Vikelsoe et al. in

1 999. In surface water (small rivers) the concentration of DINP was in all cases < 0.1 µg/l while in

v arious soils (natural and cultivated), concentrations were in the range 1 -32 µg/kg soil dw.

Howev er, in sludge amended soils the concentrations of DINP ranged from 63 to 910 µ g/kg soil dw.

A joint Nordic study measured concentrations of different plasticisers (selected phthalates as well as

others) in different aquatic media in each of the countries participating. In Denmark waste water

treatment plant (WWTP) effluent and sludge were sampled at Esbjerg central WWTP and Ejby

Mølle WWTP, Odense. Effluent was sampled at Råbylille strand WWTP, Vordingborg. Sediment

samples were collected at Vedbæk, Øresund, from Kolding Fjord and from Limfjorden. Fish

(Flounder) were sampled at Ho bugt (vicinity of Esbjerg), Hjelm bugt (vicinity of Vordingborg) and

Agersö, Great Belt. The WWTPs in Esbjerg and Odense had in 2010 loads of 115,000 and 275,000

pe (person equivalents) respectively, while the load on Råbylille Strand was much smaller, 1,100 pe.

Råby lille Strand only receives wastewater from households while the others receive from both

household and industry. The results from the study are presented in Table 47 (Remberger et al.,

2013). Note that DINP and DIDP seem to have been concentrated in the sewage sludge samples

measured.

TABLE 36

DIN P AN D DIDP CONCENTRATIONS IN SELECTED EN VIRONMEN TAL MEDIA FROM LOCATIONS IN DEN MARK,

SAMPLED IN 201 1 (FROM REMBERGER ET AL., 201 3).

Sa mple medium Loca t ion Unit DINP DIDP

WWTP effluent Esbjerg n g /l 1 60 <1 00

WWTP effluent Odense n g /l <8 0 <1 00

WWTP effluent V ordingborg n g /l <8 0 <1 00

WWTP sludge Esbjerg μ g /kg dw 5 0,000 9 ,900

WWTP sludge Odense μ g /kg dw 4 9,000 1 4,000

Sediment Ør esund μ g /kg dw 9 2 <2 0

Sediment Kolding Fjord μ g /kg dw 4 90 6 3

Sediment Limfjorden μ g /kg dw 5 9 <2 0

Fish Ho bugt μ g /kg ww <4 0 <4 0

Fish Hjelm bugt μ g /kg ww 8 7 <4 0

Fish A g ersø μ g /kg ww <4 0 <4 0


5.4 Environmental im pact

In the EU risk assessment reports for DIDP and DINP (EC, 2003a and 2003b) no additional risk

reduction measures for these two substances were found to be necessary. It should be noted

however, that the consumption of these substances has increased significantly since then.

For DMEP, Env ironment Canada (2009) finds that this substance “does not persist in the

env ironment and is not bioaccumulative”. Further, Environment Canada (2009) considers that as

“the substance is not highly hazardous to aquatic organisms and terrestrial plant and exposure

potential is low, DMEP is unlikely to cause ecological harm in Canada”.

For the other phthalates in this study no statements regarding environmental impact have been

identified.


DIPP is the only one of the phthalates in this study that has an EU harmonised environmental

classification, namely Aquatic Acute 1 (H400). A number of notifiers have provided self-

classifications of DINP and DIDP. Regarding DINP, about half of the notifiers have classified the

substance Aquatic Acute 1 + Aquatic Chronic 1 while the other half have classified it as Aquatic

Chronic 4. DIDP has been classified Aquatic Acute 1 or Aquatic Acute 1 + Aquatic Chronic 1 by

approx. half of the notifiers and Aquatic Chronic 2 by the other half.

DIDP and DINP resemble each other much with regard to chemical structure and relevant physical-

chemical properties such as water solubility, Log Kow and sorption constants, and therefore also

with regard to environmental fate and effect properties. As the water solubility of both substances is

v ery low (sub-pbb) it has only been possible to conduct tests at higher concentrations (sub-ppm)

using emulsions.

No significant acute or chronic toxic effects were observed in any tests on either of the two

substances except for a “slight but statistically significant increase in egg viability in the DINP

treated group when compared to the no treatment control” in a two-generation feeding study with

medaka (Oryzias latipes). This observation did not affect the overall conclusion by EC (2003a and

b) that DINP and DIDP are not considered to have adverse effects on the organisms (aquatic and

terrestrial) studied.

With regard to possible endocrine disruption properties it was concluded that “there is apparently

no impact on any population parameter from chronic exposure to DIDP on fish”.

DMEP is much more water soluble and a lowest experimental acute LC50 = 56 mg/l was

determined for Daphnia magna. QSAR modelling results indicate acute LC50 for fish in the range

4.3 – 452 mg/l and a lowest chronic NOEC = 14 mg/l.

Only few environmental effect data are available on the remaining substances. However, the

av ailable data do not indicate that any of them are very toxic to aquatic organisms.

All the phthalates appear to be readily biodegradable (with DMEP as a possible exception) while

abiotic processes such as hydrolysis and photolysis do not appear to be of any significance. A BCF

<1 4.4 for DIDP in fish has been determined experimentally but is considered to be too low. Instead

the BCF =860 for DEHP is recommended by EC (2003a and b) for use in risk assessment.

None of the substances are considered to meet the criteria for classification as PBT or vPvB.

The total release of DINP from waste water treatment plants to the marine areas surrounding

Denmark was estimated at around 135 kg/year.


6. Human health effects

6.1 Hum an health hazard

Different phthalates have been shown to cause a variety of effects in laboratory animals. It is

however the adverse effects on the development of the reproductive system in male animals of

certain phthalates that have raised particular concern.

In this chapter the human health aspects of the selected phthalates are evaluated. The main focus is

on the substances that are least well described in the current literature. DIDP and DINP have

recently been evaluated in relation to Entry 52 of Annex XVII to Regulation (EC) No 1907/2006

(REACH) and conclusions from this review will be cited here and only supplemented where new has

been identified.

6.1.1 Classification

Of the selected phthalates only DIPP and DMEP are subject to harmonised classification. Both

substances are classified as toxic to reproduction in category 1B. The harmonised classification is

shown in Table 37.

TABLE 37

HARMON ISED HU MAN HEALTH CLASSIFICATION ACCORDIN G TO ANNEX VI OF REGULATION (EC) N O 1 272/2008

(CLP REGU LATION )

Index No International

Ch emical

Identification

CA S No Cla ssification

Ha zard Class and

Ca tegory Code(s)

Ha zard

st atement

Code(s)

607-426-00-1 Diisopentylphthalate

(DIPP)

6 05-50-5 Repr. 1B H360FD

607-228-00-5 Bis(2-methoxyethyl)

ph thalate (DMEP)

117-82-8 Repr. 1B H360Df

The remaining phthalates are self-classified by industry with the suggested human health

classification shown in Table 12. As presented in the table, most notifiers have not classified the

substances and indicated "data lacking" and "conclusive but not sufficient for classification". The

table reflects the number of notifiers as of August 2013.

Two notifiers have suggested a classification as toxic to reproduction in category 2(Repr. 2), for

DEP and three notifiers have suggested a similar classification for DINP (CAS no. 68515-48-0). A

few more notifiers suggest that DEP should be classified for specific target organ toxicity after single

or repeated exposure. Other classification proposals reflect the acute toxicity, skin and eye irritation

potential of the substances.

For DINP it should be noted that the suggested classifications for the two different CAS numbers

are not the same. However, since only one out of 857 notifiers has suggested a classification for

DINP (CAS 28553-12-0) and four out of 269 notifiers have suggested a classification for DIDP (CAS

68515-48-0), it is not relevant to draw any conclusions on that background.


6.1.2 DEP

Kinetics and metabolism

When DEP is administrated by oral gavage the major part is metabolised into the monoester and

phthalic acid which is rapidly excreted in urine. Studies in rats and mice with 14C-DEP have shown

that 90% of the radioactivity was excreted with the urine within 48 hours with the majority being

eliminated during the first 24 hours. Approximately 3% of the radioactivity was found in faeces over

the same period of time (NICNAS, 2011).

When applied dermally , DEP penetrates the skin and is widely distributed in the body without

accumulating in tissue. In an in vitro study with human and rat skin absorption of DEP was found

to be 4.5 +/- 3 .2% through human skin based on 24 samples. With rat skin the absorption was

higher and found to be 37.5 +/- 4.0% based on 16 samples (ECHA, 2013a). In rats and rabbits it has

been shown that around 25-50% of the administered doses is excreted within 24 hours in rats and 4

day s in rabbits. Differences in dermal absorption between rats and humans may reflect species

differences, differences in vehicle and/or differences in application. NICNAS reports that results

from recent human studies indicate a dermal absorption with approximately 10% and 5.8% of

dermally applied DEP found in serum and urine, respectively within 24 hours. On a weight of

ev idence basis, NICNAS assumes a dermal bioavailability for DEP of 1 0% in humans for the

purposes of risk assessment (NICNAS, 2011).

Acute toxicity

Following oral administration of 1 4C-DEP the highest concentrations were observed in kidney and

liv er, followed by blood, spleen and adipose tissue and highest levels were noted within 20 minutes,

followed by a rapid decrease to only trace amounts after 24 h (NICNAS, 2011). Distribution in

female rabbits after dermal application of radioactively labelled DEP showed very little radioactivity

in tissues 4 days after exposure with 0.004% of the dose in the liver, 0.003% of the dose the kidney

and less than 1% of dose in the blood (NICNAS, 2011).

DEP has low acute toxicity in several animal species. LD50 values reported in rat studies range from

>5600 to 31,000 mg/kg bw (NICNAS, 2011). In rabbit an oral LD50 of 1 000 mg/kg bw is reported

but the study is not evaluated as reliable in the ECHA registration information. Dermal toxicity in

the rat is reported at >11,000 mg/kg bw and at 3000 mg/kg bw in guinea pig (NICNAS, 2011).

Irritation

Skin irritation studies are conducted in rats and rabbits. Undiluted DEP on intact and abraded

rabbit skin in a 4-hour closed patch test (duration unknown) caused irritation at both sites after 24

hours but was reduced to 40% after 72 hours. Two other studies with undiluted DEP in rabbits

under semi-occlusive conditions for 4 hours did not cause irritation. In rats application of undiluted

DEP in a semi-occlusive patch test for 2 weeks, 6 hours/day resulted in erythema and/or slight

desquamation (NICNAS, 2011). No dermal irritation was noted in 576 human subjects exposed

dermally to DEP (US CPSC, 2010).

Ov erall the available animal studies and human data suggest that DEP causes minimal skin

irritation.

Ey e irritation was studied in rabbits. Application of undiluted DEP (0.1 mL) into the conjunctival

sac of rabbit eyes resulted in transient slight redness of the conjunctivae and minimal eye irritation

in two studies (NICNAS, 2011).

The key eye irritation study in the registration dossier is an older study in rabbits considered

reliable with restrictions. 0.1 ml of 1 2.5% DEP in ethanol was installed in rabbit eyes. A severe

conjunctival irritation was seen in all 3 tested animals including chemosis and discharge. All

parameters were not fully reversible within 7 days. The results of the study were interpreted as if

DEP is moderately irritating to ey es and requires classification as irritating to eyes (Category 2)


under GHS (Regulation 1272/2008). It is noted that historical data for eye irritation of ethanol

shows similar reaction to that observed in this study (ECHA, 2013a).

Ov erall, the studies in rabbits showed that DEP causes minimal to moderate eye irritation.

Sensitisation

Skin sensitisation has been investigated using the local lymph node assay (LLNA), the Buehler test

and in the open epicutaneous test , the Draize intradermal test and the Freund’s complete adjuvant

test. There was no evidence of sensitisation to DEP in any of the tests (ECHA, 2013a; NICNAS,

2011).

DEP caused no dermal sensitization reactions in normal volunteers as well as patients, including

perfume-sensitive patients, contact dermatitis patients, children with dry plantar dermatosis, and

others. Positive patch test reactions, have been reported in patients with contact dermatitis from

ey eglasses frames and hearing aids, as well as from the plastic of a computer mouse known to

contain phthalates (NTP, 2006). Although dermal sensitisation in humans has been described it

seems to be rare.

No data on respiratory sensitisation is available.

Repeated dose toxicity

Sev eral repeated dose toxicity studies have been conducted with DEP in rats and mice via the

dermal and oral route. The liver appears to be the primary target organ for DEP in both short- and

medium-term studies. Observed effects include increased organ weight, vacuolation, elevated

serum and liver enzyme levels, and proliferation of mitochondria and peroxisomes. Hypertrophic

effects (increased volume) have also been reported in other organs such as kidney, stomach and

small intestine. The ECHA registration dossier and the NICNAS assessment both point to a 16-week

dietary study in rats as the critical study for repeated dose toxicity. In this study rats were

administered DEP in the diet at a concentrations of 0, 0.2, 1 and 5% (3,160 and 3,710 mg/kg-day for

the males and females, respectively). According to NICNAS, effects included significantly depressed

body weight (15–25% less than controls), and relative kidney and liver weights were increased

significantly in both sexes at a dose of 5% (w/w) in the diet. In females, increases in relative liver

weights were dose-dependent and statistically significant at all doses. In male rats, small intestine

weights were increased at the 5% dose only , whereas stomach weights were increased at both the 1%

and 5% dose lev els. There was no abnormal histopathology of the liver, kidney or digestive organs

and no significant effects on haematology, serum enzyme levels or urinary parameters. A

conservative NOAEL of 0.2% (corresponding to 1 50 mg/kg bw/d) was established from this study

based on dose-dependent increased relative liver weight in females and increased stomach weight

in m ales at 1% (LOAEL of 7 50-770 mg/kg bw/d) (NICNAS, 2011). This is in line with the ECHA

registration dossier.

Genotoxicity

DEP was negative in most bacterial mutagenicity tests with S. typhimurium with and without S9

activation and did not induce chromosomal aberrations in Chinese ov ary cells either with or

without exogenous metabolic activation at DEP concentrations up to 250 –324 μg/mL . DEP

induced sister chromatid exchanges in Chinese ovary cells in the presence (but not the absence) of

exogenous metabolic activation at DEP concentrations of 1 67 and 750 μg/plate (US CPSC, 2010).

Ov erall, these data do not support a genotoxic potential for DEP.

No in vivo data have been identified.

Chronic toxicity / carcinogenicity

Carcinogenicity studies are conducted in rats and mice by the oral and dermal route.


Ev aluation of 2-y ear dermal studies in mice showed a statistically significant (but not dose-related)

increase in basophilic foci in the liver in male mice dosed with 520 mg/kg bw/d. No effects were

reported in female mice. Marginally increased incidences of combined hepatocellular adenomas and

carcinomas were noted in both sexes but they were statistically significantly dose-related only in

male mice. Due to lack of dose-response relationship in female mice and similar incidences of

hepatocellular neoplasms between the high dose male mice and historical controls, these increases

were considered equivocal evidence of carcinogenic activity for DEP (NICNAS, 2011).

In similar 2-year dermal studies in rats, no evidence of increased neoplasia was found other than

treatment-related epidermal acanthosis (specific type of hyperpigmentation) at sites of DEP

application, which was considered an adaptive response to irritation. No other lesions or neoplasms

were noted in these 2-year studies in mice and rats. DEP did also not demonstrate any initiating or

promoting activity in additional studies (NICNAS, 2011).

Ov erall, it is concluded that available data do not support a carcinogenic potential for DEP.

Reproductive toxicity

Sev eral studies have been conducted with DEP in rats and mice to investigate reproductive toxicity

endpoints. An ov erview is presented in NICNAS (2011) is shown in Table 45.

TABLE 38

OVERVIEW SUMMARY OF THE FERTILITY AND DEVELOPMEN TAL EFFECTS OF DEP (N ICNAS, 201 1)

Study design Species /

route

Doses

(mg/kg bw/d)

NOAEL

(mg/kg bw/d)

LOAEL

(mg/kg bw/d) and

endpoint

References from

NICNAS (2011)

Multigenerational dietary reproductive toxicity studies

1 8 weeks (1 week prior to mating till weaning) 20/sex/group

Mice CD-1 Diet

0, 0.25, 1.25, 2 .5% (0, 340, 1 770, 3640)

Maternal: 3640 (F0) NE (F1 )

Fertility-related parameters: 3640 (F0) NE (m, F1 ) 3640 (f, F1) Dev elopmental: 3640 (F1) NE (F2)

Maternal:

3640 (F1): body

weight (m-f); liver &

pituitary weights (f)

Fertility-related parameters:

3640 (m, F1): sperm counts, prostate weight

Dev elopmental:

3640 (F2): no. of live pups/litter (combined sexes)

Lamb et al., 1 987

1 5-17 weeks per generation (10 weeks prior to mating till weaning)

24/sex/group

Rats

SD

Diet

0, 600, 3000, 15 000 ppm (0, 40-56, 197-267, 1 016-1375) (m-f)

Maternal:

1 97-267 (m-f, F0, F1 )


40 (m, F0, F1)

1 375 (f, F0, F1 )

Maternal:

1 016-1375 (m-f):

liv er weight (F0, F1); kidney weight (f, F1)


1 97 (m): serum testosterone (F0),

abnormal and tailless sperms (F0, F1)

Dev elopmental:

Fujii et al., 2005



route

Doses

(mg/kg bw/d)

NOAEL

(mg/kg bw/d)

LOAEL

(mg/kg bw/d) and

endpoint

References from

NICNAS (2011)

Dev elopmental:

1 97-267 (m-f, F1 , F2)

1 016-1375 (m-f): pup weight on PND 21 (F1, F2) and PND 4-21 (f, F1 ), delayed pinna detachment (m, F1) & v aginal opening (f, F1)

Studies on testes and testicular function

4 day s 1 2/group

Rats Male SD Intubation

0, 1 600 Fertility-related parameters: 1 600

NE Foster et al., 1 980

7 days 1 0/group

Rats Male Wistar Diet

0, 2% (~2000) NE Fertility-related parameters:

2000: serum and testis testosterone

Oishi & Hiraga, 1 980

2 days 1 2/group

Rats Male Wistar Gav age

0, 2000 NE Fertility-related parameters: 2000: ultrastructural changes in Leydig cells

Jones et al., 1 993

1 50 days 6/group


0, 1 0, 25, 50 ppm (0, 0.57, 1 .43, 2 .85)

NE Fertility-related parameters:

0.57: testis weight, testicular antioxidant enzy mes, serum testosterone and androstenedione

Pereira et al., 2008b ND

28 days 6/group

Rats Male SD Gav age

0, 250 (MEP) NE Fertility-related parameters: 250: sperm counts & motility

Kwack et al., 2009 ND

7 days 1 0/group


0, 2% (~2000) NE Fertility-related parameters: 2000: serum and testis testosterone

Foster et al., 1 980

2 days 1 2/group

Rats Male Wistar Gav age

0, 2000 NE Fertility-related parameters: 2000: ultrastructural changes in Leydig cells

Oishi & Hiraga, 1 980

Prenatal developmental toxicity studies

GD 5, 1 0, 15 5/group

Rats SD ip

0, 0.51, 1.01, 1 .69 mL/kg (0, 500, 1000, 1 500)

NE Developmental: 500: pup weight,

skeletal abnormalities

Singh et al., 1 972

GD 0-1 7 1 7-20/group

Mice Jcl:ICR Dermal

0, 500, 1600, 5600

Maternal: 1 600 Developmental: 1 600

Maternal: 5600: adrenal and kidney weights Developmental: 5600: pup weight,

skeletal variations (rudimentary cervical and lumbar ribs)

Tanaka et al., 1 987* (reviewed by SCCNFP, 2002; IPCS, 2003)

GD 6-1 3 Mice 0, 4500 Developmental: NE Hardin et al., 1 987



route

Doses

(mg/kg bw/d)

NOAEL

(mg/kg bw/d)

LOAEL

(mg/kg bw/d) and

endpoint

References from

NICNAS (2011)

50/group CD-1 Gav age

4500

GD 6-1 5 27 -32/group

Rats CD Diet

0, 0.25, 2 .5, 5% (0, 200, 1900, 3200)

Maternal: 200 Developmental: 1 900

Maternal:

1 900: body weight & food consumption Developmental:

3200: skeletal v ariations (rudimentary lumbar ribs)

Field et al., 1 993

GD 1 2-19 5/group

Rats CD Gav age

0, 500 Developmental: 500

NE Liu et al., 2005

GD 8-1 8 5/group

Rats SD Gav age

0, 1 00, 300, 600, 900

Maternal: 900 Developmental: 900

NE Howdeshell et al., 2008 ND

Postnatal developmental toxicity study (one-generation study)

GD 1 4 - PND 3 5/group

Rats SD Gav age

0, 7 50 Developmental: 7 50

NE Gray et al., 2000

F0 = parental generation; F1= first filial/offspring generation; F2 = second filial/offspring generation; m -f = male-female; ip = intraperitoneal; no. = number. = decreased; = increased; GD = g estational day; NE = not established; PND = postnatal day; SD = Sprague-Dawley * Qu oted as secondary citations from the key documents listed in Section 1.3; ND = n ew data since the release of the NICNAS DEP Hazard Assessment in 2008.

With regard to fertility parameters, it is concluded that associations are drawn between exposure to

DEP and abnormal sperm parameters but no ev idence of effects leading to decreased fertility in

animals. Based on the multigeneration dietary reproductive toxicity study in rats NICNAS (2011)

established NOAEL of 40 mg/kg bw/d was for fertility-related parameters based on the reduced

testosterone levels and the increased incidence of abnormal sperms at 197 mg/kg bw/d.

Based on the same study, NICNAS (2011) concludes that the developmental NOAEL was 197 mg/kg

bw/d and the LOAEL was 1016 mg/kg bw/d based on decreased pup weight and developmental

delay.

Based on the same study in the registration dossier for DEP, the registrant has suggested a NOAEL

for general toxicity and reproductive performance in parental animals at 15000 ppm (1016 mg/kg

bw/d) as there were no adverse effects on these parameters. For development and growth of pups

the NOAEL is considered to be 3000 ppm (197 mg/kg bw/d) due to decreased body weight gain in

those given 15000 ppm (ECHA, 2013).

Endocrine disruption

The Danish Centre on Endocrine Disrupters (CEHOS, 2012) has provided a science based

ev aluation of the endocrine disrupting properties of the 22 substances on the SIN list 2 version 2.0.

DEP is one of the substances which have been evaluated against the proposed Danish criteria for

endocrine disrupters. The criteria are shown in Appendix XX. The result of the evaluation with

relevance for human health was according to CEHOS (2012):

2 List of substances identified by the NGO ChemSec as Substances of Very High Concern (SVHC) according to the criteria in REACH. http://www.chemsec.org/what-we-do/sin-list/sin-list-20

http://www.chemsec.org/what-we-do/sin-list/sin-list-20


Di-ethyl phthalate (DEP), CAS 84-66-2

Associations between DEP exposure and clinical outcomes related to endocrine disruption (AGD in

boys, infertility, and insulin resistance) have been reported in human studies. For some outcomes

the same associations were seen as well for other phthalate metabolites present at the same time.

Some in vitro studies show weak estrogenic effects, whereas others do not, i.e. results are

conflicting.

In experimental animals findings of reduced testosterone levels, delayed vaginal opening and

increased incidence of abnormal sperm in a two-generation study point to endocrine disruption.

Several studies show that DEP does not share the same mode of action as DEHP, DBP, BBP, DPP

and DiBP and does not affect e.g. anogenital distance, fetal testosterone production, fetal

testicular gene expression, nipple retention, and reproductive organ weights. Two other studies

describe effects of DEP on semen quality, but it is not the same parameters that are alteretered in

the three studies. Other studies including an enhanced 28-day study did not detect any sperm

quality changes. Thus, the possibility of effects of DEP on sperm quality is controversial and

although evidence of endocrine disruption has been shown, any evidence of adverse effects is less

clear.

Evaluation: Suspected ED in Category 2a.

Category 2a – Suspected ED

Substances are placed in category 2a when there is some ev idence from humans or

experimental animals, and where the evidence is not sufficiently convincing to place the

substance in category 1. If for example limitations in the study (or studies) make the quality of

ev idence less convincing, category 2a could be more appropriate. Such effects should be

observ ed in the absence of other toxic effects, or if occurring together with other toxic effects,

the ED effect should be considered not to be a secondary non-specific consequence of other

toxic effects. Substances can be allocated to this category based on:

- Adv erse effects in vivo where an ED mode of action is suspected - ED mode of action in vivo that is suspected to be linked to adverse effects in vivo - ED mode of action in vitro combined with toxicokinetic in vivo data (and relevant non

test information such as read across, chemical categorisation and QSAR predictions).

6.1.3 DIPP

The following data is available in the registration dossier for DIPP (ECHA, 2013):

LD50, oral in rat: >2000 mg/kg bw

Not irritating in EPISKIN three dimensional human skin model

Non corrosive/non severe eye irritant in Bovine Corneal Opacity and Permeability Test: An In

Vitro Assay of Ocular Irritancy

Sensitising in Mouse local lymphnode assay (LLNA). Considered a potential skin sensitiser

Negative in Mutagenicity - Rev erse Mutation Test Using Bacteria (s. typhimurium) with and

without metabolic activation

DIPP is subject to harmonised classification and evaluated as requiring classification for

reproductive toxicity in category 1B.


In Annex I to the Annex XV dossier, proposing DIPP a s a SVHC substance, the following additional

information is available (Environment Agency Austria, 2012):

A good skin penetration potential can be expected as for the structurally related diisobutyl

phthalate about 10 %

Absorption via the gastrointestinal tract is substantiated by systemic effects in animal

experiments. Alkyl phthalates are assumed to be absorbed via the respiratory tract. Since the

v apour pressure is very low, inhalative exposure is only to be expected if DIPP is strongly

heated or if aerosols are formed.

Studies regarding metabolism of DIPP are not available

With regard to developmental toxicity and effects on fertility, the following information is available

(Environment Agency Austria, 2012):

According to recent and older studies there is strong evidence that dipentylphthalate (CAS 131-

1 8-0) is an equal or even more potent testicular toxicant than DEHP. This is likely to be valid

also for other structurally related pentyl phthalates, like DIPP. This is supported by results of

from 1 997. The mixture of pentyl phthalates caused a 100 % resorption at 1000 mg/kg/day

while DEHP caused malformations in 70% of the litters at the same dose.

There are no studies on fertility with DIPP av ailable to date. A fertility reducing action is

suspected because of the structural relationship to di-n-pentyl phthalate and dibutylphthalate

and the findings available for these substances. The monoesters of phthalic acid esters of

medium chain length (C4 – C6) cause damage to the germinal epithelium in the test is. Sertoli

cells in the seminiferous tubules are the primary site of attack. They exhibit considerable

v acuolization of the smooth endoplasmatic reticulum resulting in a reduced fertility. As a

consequence the germinal epithelium may be lost. (ECBI/65/00 Add2).

No further information has been identified.

6.1.4 DPHP

The following data is available in the registrations dossier for DPHP (ECHA, 2013):

The registration dossier reports results from a study of excretion following oral administration

of DPHP in a healthy 63 year old male human volunteer. After a single oral application DPHP

was hydrolysed to the respective monoester, which underwent further metabolic changes. 34 %

of the applied dose was excreted in the urine, most of it as secondary metabolites. Only a

minute amount of the applied dose was excreted in the form of the monoester (less than 1 %).

It is noted that most of the metabolites were excreted within the first 24 hours after the dosing.

LD50, oral in rat: >5000 mg/kg bw

LC50: >5 mg/L air (4 hours). Clinical signs: Immediately after exposure the animals were wet,

ruffled, agitated and raspy sounding. After 24 hours they appeared normal.

LD50, dermal in rabbit: >2000 mg/kg bw. Clinical signs: There were no unusual behavioural

signs noted.

Not irritating to skin in rabbits according to EPA OPPTS 870.2500 (Acute Dermal Irritation)

Non irritating to rabbit eyes according to OECD Guideline 405 (Acute Eye Irritation /

Corrosion)

Not sensitising in guinea pigs according to modified Buehler-test with 10 inductions

Not sensitising in QSAR calculation


The NOAEL in a repeated dose toxicity test in rats was established at 39 mg/kg bw/day based

on effects on liv er weight (peroxisomal proliferation) according to OECD Guideline 408

(Repeated Dose 90-Day Oral Toxicity in Rodents)

Negative in chromosome aberration test according to OECD Guideline 473 (In vitro

Mammalian Chromosome Aberration Test)

Negative in Mutagenicity - Rev erse Mutation Test Using Bacteria (s. typhimurium) with and

without metabolic activation according to OECD Guideline 471 (Bacterial Reverse Mutation

Assay)

Negative in Chinese Hamster Ovary (CHO) cell gene mutation assay according to OECD

Guideline 476 (In vitro Mammalian Cell Gene Mutation Test)

A NOAEL of 8000 ppm (479.2 mg/kg bw/day (males); 619.6 mg/kg bw/day (females)) was

established in a supporting carcinogenicity study based on organ weight and histopathology.

Read-across from other high molecular weight (HMW) structural analogue s

(DINP/DIDP/DEHP/Di-C1 1 PE).The members of this category did not show potential for

producing genetic effects. Liver tumours induced by peroxisome proliferation in rodents by

HMW phthalate esters are not considered relevant in humans (ref. to SIDS, 2004).

A NOAEL of 40 mg/kg bw/day (general systemic toxicity) was established in a Two-

Generation Reproduction Toxicity Study in the rat according to OECD Guideline 416 based on

peroxisome proliferation in the liver, bones, kidneys and thyroid; body weight; food

consumption and compound intake. NOAEL for fertility was established at 600 mg/kg bw/day

in parental and F1 animals based on ov erall effects; organ weights; histopathology; mating

index; and fertility index. NOAEL in F1 and F2 animals was established at 200 mg/kg bw/day

based on decreased pup body weights/pup weight gain. In conclusion DPHP did not influence

fertility or reproductive parameters in parental animals and offspring.

A NOAEL of 200 mg/kg bw/day for embryotoxicity, foetotoxicity and maternal toxicity was

established in a developmental toxicity study in rats according to OECD Guideline 414

(Prenatal Developmental Toxicity Study). The NOAEL for teratogenicity was established at

1 000 mg/kg bw/day. In a similar study with less animals the NOAEL for embryotoxicity,

foetotoxicity, maternal toxicity and teratogenicity was established at the highest dose of 1 000

mg/kg bw/day.

The Unites States Consumer Product Safety Commission (USCSPC, 2010) has assessed the

potential health effects on consumers under the risk-based Hazardous Substances Act (FHSA)

based on v ery much the same information as in the publicly available registration information for

acute, repeat dose and reproductive and prenatal, perinatal, and post -natal toxicity. The ov erall

conclusion was that an insufficient amount of animal data and poorly described methodologies in

studies using DPHP as a test substance supported the conclusion that there was "insufficient

ev idence" for the designation of DPHP as a "hepatotoxicant", "adrenal toxicant", reproductive

toxicant" and "developmental toxicant". No ADI was estimated for the general population or for

other sensitive sub-populations because of lack of confirmatory data.

6.1.5 DMEP

No REACH registration dossier is available for DMEP.

Kinetics and metabolism

There is limited information about the toxicokinetics of DMEP. Studies in pregnant rats have shown

that DMEP is hy drolysed to MMEP (mono-2-methoxyethyl phthalate) and 2 -ME (2-

methoxyethanol). 2-ME is further oxidised to MMA (methoxyacetic acid). DMEP injected

intravenously is rapidly transferred across the placenta into the foetus which has little or no ability

to hydrolyse DMEP to the monoester (NICNAS, 2008).


Based on an in v itro assay, DMEP is predicted to absorb very slowly into human skin, with a steady

state absorption rate of 8 µg/cm2 /hour (USCPSC, 2011).

Acute toxicity

DMEP has low acute, dermal and inhalational toxicity. The oral LD50 in rats was reported to be

3200 – 6400 mg/kg bw (NICNAS, 2008). The dermal LD50 was > 11,710 mg/kg bw in guinea pigs

(Environment Canada, 2009). LC50 (6 h) in rats was reported at > 770-1595 ppm (NICNAS, 2008).

Irritation

Based on a study in guinea pigs, where DMEP caused slight skin irritation when applied to

depilated guinea pig abdomen under occlusive wrap for 24 hours, it was concluded that DMEP

caused minimal skin irritation in guinea pigs. The same conclusion was made regarding eye

irritation based on studies where DMEP was applied to rabbits eyes (NICNAS, 2008). No data

regarding respiratory irritation have been identified. Due to DMEPs v ery low vapour pressure

respiratory irritation is not expected.

Sensitisation

DMEP did not elicit a positive response when administered to ten guinea pigs using a standardised

sensitisation procedure, but without further details of the test conditions (NICNAS, 2008)

Repeated dose toxicity

In subchronic repeated dose studies, DMEP caused decreases in absolute and relative thymus and

testes weight with histological evidence of testes atrophy in rats (1000 mg/kg bw/day, gavage) and

decreased relative testes weight in mice (250 mg/kg bw/day, intraperitoneal). In a rat 16-day

gavage study, a LOAEL of 1 00 mg/kg bw/day was established based on decreases in haemoglobin

and haematocrit values. No NOAEL could be established (NICNAS, 2008).

Genotoxicity

DMEP did not cause a significant increase in reverse histidine mutations in the presence of

metabolic activation when treated in the in vitro Ames reverse mutation assay in Salmonella

typhimurium strains ester strains TA98 and TA100 at concentrations up to 1 0,000 µg/plate with

and without metabolic activation. With no activation, positive results were obtained in strain TA98

(US CPSC, 2011).

The genotoxicity of DMEP was also assessed in the in vivo dominant lethal assay. The high dose of

DMEP statistically reduced the incidence of pregnancies and the number of implants per pregnancy

compared to the control group, indicating a dominant lethal effect at this dose of 2785

mg/kg bw (US CSPC; 2011).

Chronic toxicity / carcinogenicity

A fiv e-generation oral study with very limited study details did not reveal any chronic effects

induced by DMEP in rats. The actual dosage was not stated and the dose was therefore estimated

based on the assumption that DMEP was applied to rats in diet and administered up to 900 mg/kg

diet per day (45 mg/kg bw per day). No signs of reproductive toxicity or carcinogenicity were

observ ed in this old study from 1968 (Environment Canada, 2009). Carcinogenicity relevant for

humans has also not been recognized for 2-ME (2- Methoxyetahnol) or other glycol ethers Although

some phthalates induced various tumours in experimental animals, the relevance of these data to

DMEP carcinogenicity and to humans is unclear (Environment Canada, 2011).

Reproductive toxicity

DMEP is subject to harmonised classification as toxic to reproduction in category 1B.


A NOAEL of 1 00 mg/kg for reproductive organ toxicity was established from an oral repeat dose

study in rats based on decrease in testes weight at 1000 mg/kg bw/d. However, no reproductive

toxicity studies were performed according to OECD guidelines (NICNAS, 2008).

There were no developmental studies following oral or inhalation administration of DMEP.

Intraperitoneal injection induced marked embryotoxic, fetotoxic and teratogenic effects at doses

abov e 1.03 mmol/kg (estimated 291 mg/kg bw). A NOAEL could not be established due to

teratogenic effects at the lowest dose. The effects on the dams were unreported. Both 2 -ME and

MAA induced malformations, principally skeletal, in developmental studies. Overall, from available

studies, it is anticipated that DMEP may cause fertility and developmental effects (Cited from

NICNAS, 2008).


In relation to the current re-assessment of the safety aspects of phthalates, e.g. DEHP, used in

medical devices by the Scientific Committee on Emerging and Newly Identified Health Risks

(SCENIHR) the Danish Ministry of Health has in 2012, encouraged the European Commission to

consider having the SCENIHR study include an additional five phthalates suspected of having

endocrine disrupting effects, including DMEP. The re-assessment is expected to be finalised early

2014 (Danish EPA, 2013).

No further information on endocrine disruption has been identified.

6.1.6 DINP and DIDP

DINP and DIDP are more extensively reviewed than the other selected phthalates for this study. In

August 2013 ECHA issued a final review report with an Evaluation of new scientific evidence

concerning DINP and DIDP in relation to entry 52 of Annex XVII to REACH Regulation (EC) No

1 907/2006 (ECHA, 2013). Conclusions from this r eview are presented in the following (references

included in the cited sections belong to the ECHA review).

Kinetics

Based on read-across from DEHP, it is assumed that humans orally absorb DINP and DIDP

100%. The oral absorption in adult rats was estimated to be in the order of 50-55%.

A bioavailability factor of 75% for inhalation can be assumed for adults and 100% for newborns

and infants as a vulnerable subpopulation.

Based on a study with DEHP (Deisinger et al. 1998), and the assumption that

DINP and DIDP are 10 times less absorbed through the skin than DEHP (Elsisi et al. 1989), a

dermal absorption rate of 0.024 μg/cm2/h can be assumed.

Acute toxicity

Conclusions from the EU risk assessments are still considered valid:

DINP: “Most of the animal studies on acute toxicity were either not available for detailed study or

performed prior to establishment of OECD or EU guidelines. However given the consistency of the

results for oral, dermal and inhalation exposure, it can be considered that DINP has a low acute

oral, dermal and inhalation toxicity. No LD50/LC50 was reported from acute exposure by those

routes of exposure. Findings consisted of poor state, respiratory difficulties (laboured respiration,

dyspnea) and alteretered appearance, following oral administration, even at very high level (up

to 40,000 mg/kg). Acute inhalation studies, although poorly documented, did not report any body

weight changes, any gross lesions or microscopic alterations of lungs, only slight tearing of the

eye and slight clear nasal discharge following aerosol exposure of 4.4 mg/l of air during four

hours. Therefore, no classification is indicated according to the EU criteria for acute toxicity.” (EC

2003a).


DIDP: “Most of the animal studies on acute toxicity were either not available as detailed studies or

performed prior to establishment of OECD or EU guidelines. However in view of the consistency

of the results for all routes of exposure, it can be considered that DIDP has a low acute oral,

dermal and inhalation toxicity. No classification is indicated according to the EU criteria for acute

toxicity whatever the route of exposure.” (EC 2003b)

Irritation and corrosivity


DINP: “On the whole, DINP may be considered as a very slight skin and eyes irritant, with effects

reversible in short time. Thus no classification is indicated according to the EU criteria for those

different end points.” (EC, 2003a)

DIDP: “Results from animal studies following single skin exposure varying from 5 minutes to 24

hours lead to no or moderate effect, reversible with possible desquamation. Effects on eyes are

weak and limited to conjunctiva. There is no indication of upper airways irritation in animal. In

humans there is no indication of an irritating potential. Thus no classificationis indicated

according to the EU criteria for those different end points.” (EC 2003b) .

Sensitisation - DINP and DIDP

In general, phthalates (including DINP and DIDP) lack intrinsic sensitising potential. However,

both DINP and DIDP share at least some of the adjuvant properties demonstrated for phthalates

and an effect on atopic responses in humans cannot be excluded. An association has been shown

between exposure to phthalates and asthma and allergic disease in epidemiological studies.

However, a causal relationship remains to be established.

Repeated dose toxicity - DINP

A NOAEL of 15 mg/kg bw/day with a LOAEL of 152 mg/kg bw/day (Exxon 1986) and a NOAEL of

88 mg/kg/day with a LOAEL of 359 mg/kg bw/day (Aristech 1994) were identified in the two key

repeated dose toxicity studies based on statistically significant increases of incidence of spongiosis

hepatis together with other signs of hepatotoxicity.

As a result of the methodological difference (amount of examined liver sections), the Exxon (1986)

study was considered the most appropriate to use. Thus a NOAEL of 15 mg/kg bw/day was

selected for repeated dose toxicity of DINP. This conclusion was supported by RAC (ECHA 2013a).

RAC however noted that the NAEL could be higher given the large dose spacing in the Exxon

study.

Repeated dose toxicity - DIDP

Subchronic studies in respectively the dog (Hazleton 1968b) and rat (BASF 1969) were available.

From the rat study, a NOAEL of 60 mg/kg bw/day can be as sumed based on dose-related

increase of relative liver weights in females. A NOAEL of 15 mg/kg bw/day can be derived for the

study in dog on the basis of hepatic effects. However, the large limitations of the study need to be

emphasised.

In a new 2-year rodent carcinogenicity study by Cho et al. (2008, 2010) a LOAEL of 22 mg/kg

bw/day based on spongiosis hepatis in a 2-year study in rat could be derived. However, there are

some questions related to the reliability of these findings.

In line with the opinion of RAC (ECHA 2013a,b), a weight of evidence approach was used for

DNEL calculation on the basis of a LOAEL of 22 mg/kg bw/day (Cho et al. 2008, 2010), a NOAEL

of 15 mg/kg bw/day (Hazleton 1968b) and a NOAEL 60 mg/kg bw/day (BASF 1969b).


Mutagenicity


“DINP is not mutagenic in vitro in bacterial mutation assays or mammalian gene mutation assay

(with and without metabolic activation) and is not clastogenic in one cytogenetic assay in vitro on

CHO cells and in one in vivo assay on bone marrow cell of Fisher 344 rats. This suggests that

DINP is not genotoxic in vivo or in vitro.” (EC 2003a)

“DIDP is not mutagenic in vitro in bacterial mutation assays (with and without metabolic

activation) and is negative in a mouse lymphoma assay. It is not clastogenic in a mouse

micronucleus assay in vivo. This indicates that DIDP is a non-genotoxic agent.” (EC 2003b)

Carcinogenicity – DINP

The renal tumors seen in rats are assumed to stem from an alpha-2u-globulin mode of action

which is not considered to be relevant for humans.

Liver neoplasia were seen in rats and mice with a NOAEL of 112 mg/kg bw/day. It is believed that

peroxisome proliferation is the underlying mode of action for development of liver tumors with

DINP, and that PPARα3 is involved in hepatic tumour formation. However, the more recent

literature indicates that the mechanisms of liver carcinogenicity in rodents with peroxisome

proliferators have not entirely been elucidated and that multiple pathways seem to exist. Some of

those pathways seem to be PPARα-independent, which might indicate a need for some caution

when interpreting the relevance of rodent carcinogenicity with DINP to humans.

The increased incidences in MNCL (mononuclear cell leukemia) seen in rats with a NOAEL of 15

mg/kg bw/day might have a human counterpart. The available information does not allow to

draw definite conclusions on the relevance of the findings. As MNCL is likely to follow a threshold

mode of action with a NOAEL equal to that for repeated dose toxicity, the finding would not be a

driver for the risk assessment. Therefore, the endpoint is not taken further to the risk

characterisation step.

Carcinogenicity – DIDP

Although no treatment-related tumours were observed in a 2-year carcinogenicity study with

rats, DIDP has been shown to induce liver adenomas in a 26-week study in rasH2 mice (NOAEL of

0.33% in feed, estimated to correspond to approximately 500 mg/kg bw/day). I t is assumed that

the increased incidence of liver adenomas in mice is related to peroxisome proliferation, and that

PPARα is involved in hepatic tumour formation. However, the more recent literature indicates

that the mechanisms of liver carcinogenicity in rodents with peroxisome proliferators have not

entirely been elucidated and that multiple pathways seem

to exist. Some of those pathways seem to be PPARα-independ nt, which might indicate a need for

some caution when interpreting the relevance of rodent carcinogenicity with DINP to humans.

The increased incidences in MNCL seen in a 2-year carcinogenicity study with rats (NOAEL of 110

mg/kg bw/day) might have a human counterpart. The available information does not allow to

draw definite conclusions on the relevance of the findings. As MNCL is likely to follow a threshold

mode of action with a NOAEL well above that for repeated dose toxicity, the finding would not be

a driver for the risk assessment. Therefore, the endpoint is not taken further to the risk

characterisation step.

3 PPAR = peroxisome proliferator activated receptor


Reproductive toxicity- DINP

Decreases foetal testicular testosterone concentration during critical time window of

masculinisation and increased incidence of multinucleated gonocytes and Leydig cell aggregates

were observed with a NOAEL of 50 mg/kg bw/day. In a two-generation reproductive toxicity

study the offspring bodyweight was decreased with a LOAEL of 159 mg/kg bw/day (no NOAEL)

and increased skeletal variations were observed in a prenatal developmental toxicity study with a

NOAEL of 100 mg/kg bw/day. The in vivo findings indicate that DINP has anti-androgenic

potency but may also exhibit its effects through other modes of action.

Effects on fertility occur at higher dose levels, with a NOAEL for decreased live birth and survival

indices of 622 mg/kg bw/day and a NOAEL of 276 mg/kg bw/day for decreased testicular

weights.

Reproductive toxicity - DIDP

The most critical reproductive effect for DIDP is the decreased survival of F2 pups observed in

both two-generation reproductive toxicity studies with rats, leading to a NOAEL of 33 mg/kg

bw/day. A NOAEL of 40 mg/kg bw/day can be derived for foetal variations from prenatal

developmental toxicity studies.

DIDP did not induce substantial anti-androgenic activity in available studies; in particular it did

not reduce foetal testicular T levels or affect gene expression levels related to masculinisation

during critical time window during development. DIDP seems to have a partly different spectrum

and/or potency of toxicological properties than several other phthalates, such as DINP, DEHP

and DBP.

Other effects on fertility occurred at higher doses with a NOAEL of 427 mg/kg bw/day (0.8%

dietary level) based on a two-generation reproductive toxicity study.


The ECHA review concludes regarding estrogenic activity that DIDP and DINP do not seem to be

active. It is however noted that certain phthalates, such as DEHP, have suggested affecting also

female reproductive health but as whole the effects of phthalates on reproduction in females have

been studied much less than in males (ECHA, 2013).

The ECHA review also emphasises that for both males and females, other relevant human health

endpoints concerning endocrine disruption such as developmental neurotoxicity, thyroid system,

arylhydrocarbon receptor signalling and obesity have not been clearly associated with phthalate

exposure according to other recent reviews.

According to the Danish Phthalate Strategy (Danish EPA, 2013) Denmark will in 2013 assess

whether the evidence of endocrine disrupting effects observed at high doses of DINP prov ides a

basis for a harmonised classification or other measures (Danish EPA, 2013).

6.2 Hum an exposure

Humans are potentially exposed to phthalates through ingestion, inhalation, and dermal contact.

Quantification of the exposure can be based on indirect methods where the exposure is based on

estimations of the concentration of phthalates in different sources (air, soil, diet, articles, etc.) or

direct methods based on results from biomonitoring studies of relevant biomarkers.

According to Clark et al. (2011), the indirect and biomarker methods generally are in agreement

within an order of magnitude and discrepancies are explained by difficulties in accounting for use of

consumer products, uncertainty concerning absorption, regional differences, and temporal changes.

No single method is preferred for estimating intake of all phthalate esters. It is suggested that


biomarker estimates be used for low molecular weight phthalates for which it is difficult to quantify

all sources of exposure and either indirect or biomarker methods be used for higher molecular

weight phthalates. The indirect methods are useful in identifying sources of exposure while the

biomarker methods quantify exposure (Clark et al., 2011).

For the selected phthalates, most data are available for DINP, DIDP and DEP. As DMEP is not on

the market in Europe exposure is expected to be related to imported articles only.

6.2.1 Direct exposure pathways

Based on the identified uses in Denmark for the selected phthalates, possible direct exposures are

suggested in Table 39.

TABLE 39

OVERVIEW OF POSSIBLE DIRECT EXPOSURE FROM THE SELECTED PHTHALATES IN DENMARK

Ph tha-

late

Con su m ers Working env iron m ent

Rou t e Sou rce Rou t e Sou rce

DINP Dermal, ingestion,

in halation (dust)

V arious flexible PVC products

in doors and outdoors (by

touch, ingestion of foods

pa cked or kept in plasticised

food contact plastics

Dermal, inhalation

(dust, aerosols)

V arious flexible PVC products

in doors and outdoors, sealants

a n d paints (by application and

oth er handling)

DIDP Dermal, inhalation

(dust)

Wire and cable, tarpaulins (at

a pplication and other

h andling)

Dermal, inhalation

(dust, aerosols)

Wire and cable, tarpaulins, roof

m embranes, geo-membranes,

sea lants, paints (by application

a n d other handling)

DPHP do do do do

DEP Dermal, ingestion,

in halation

(a erosols)

Cosmetics and personal care

pr oducts (+others?); at

per sonal use or indirectly at

con tact with persons using

th em

Dermal, ingestion,

in halation aerosols

Cosmetics and personal care

pr oducts (+others?) from

per sonal use or indirectly by

con tact with persons using them

DIPP - - Dermal Ex plosives?

DMEP - - - -

Leg end: - : Exposure deemed absent or marginal; ?: Uncertain, cannot be ruled out complete ly;

The Danish eight-hour average occupational exposure limits for DEP, DINP (CAS No. 28553-12-0)

and DIDP (CAS No. 26761-40-0) are 3 mg/m3 workplace air.

6.2.2 Indirect exposure pathways

Based on the identified uses in Denmark for the selected phthalates, possible indirect exposures are

suggested in Table 40 based on general background knowledge.


TABLE 40

OVERVIEW OF POSSIBLE INDIRECT EXPOSURE FROM THE SELECTED PHTHALATES IN DENMARK

Ph tha-

late

Indoor

climate

V ia ext erna l env iron m ent Rem a rks

Food and

drink

A ir Soil Wa t er

DINP X X - - - V arious product uses (via evaporation + dust)

DIDP X - - - - Wire and cable (via evaporation + dust)

DPHP x - - - - Wire and cable (via evaporation + dust)

DEP x - - - - Cosmetics and personal care products (via

ev aporation + dust)

DIPP - - - - - Use may be limited to some explosives and some

a mmunition charges; no data indicating

significant environmental concentrations were

fou nd

DMEP ? ? - - - Ma y be contained in im ported articles, but

ex posure is expected to be limited; no data

in dicating significant environmental

con centrations were found

Leg end: X : Possible exposure; x: possible exposure, but likely smaller relatively; ?: Uncertain, cannot be ruled

ou t completely; - : Exposure deemed absent or marginal.

Indirect exposure of v ulnerable groups to DINP considering Danish exposure situations are

estimated in two recent projects from the Danish EPA.

In a survey and health assessment of the exposure of 2 -year-olds to chemical substances in

consumer products (Danish EPA, 2009) the contribution from foods is estimated at a maximum of

1 0 µg/kg bw/day of DINP and the contribution to ingestion of DINP from the indoor climate (dust

and air) is estimated at 0.0003 µg/kg bw/day (worst case/winter scenario based on ingestion of 100

mg dust).

In a project on exposure of pregnant consumers to suspected endocrine disruptors (Danish EPA,

2012) the exposure of women in the child-bearing age to a number of suspected endocrine

disruptors including DINP was investigated. The total, maximum exposure from consumer

products, indoor environment and food was estimated at 2 .2042 µg/kg bw/day.

No data specific for Danish conditions on the other selected phthalates were identified.

DMEP is not registered for use in Europe but may be imported in articles containing e.g. cellulose

acetate lamination films. The Annex XV dossier for DMEP (BAUA, 2011) includes a reference to

recent Austrian unpublished results where DMEP was analysed in 10 products and 10 house dust

samples (commercial and private) and was not detected above the detection level of 0.04 mg/kg.

DMEP has been detected in an older German study conducted in 65 apartments in Hamburg,

Germany between 1998 and 2000 and analysing indoor dust (<63 µm) collected from vacuum

cleaner bags. DMEP was detected in 49 samples in concentrations up to 17 mg/kg (50th percentile

= 2 mg/kg; 95th percentile = 8 mg/kg) and it was speculated that the phthalates originated from

use of consumer products.


6.3 Bio-m onitoring data

For phthalates most biomonitoring studies used for estimation of exposure have investigated levels

of metabolites in urine and to a much lesser extent levels in blood and breast milk. Although parent

phthalates can be detected in blood, fa st cleavage of the first ester bond by serum esterase, results in

a v ery short half-life, which makes the parent compound unsuitable as a biomarker (ECHA, 2013).

Urinary concentrations in nursing mothers are not considered useful for estimating exposure to

phthalates through milk ingestion by breast-fed infants (Högberg et al., 2008)

Danish biomonitoring data specifically relevant for the phthalates selected for this study have been

identified for DINP and DEP.

DINP and DIDP

Danish biomonitoring data are available for DINP. Estimated DINP intakes (µg/kg bw/day) based

on urinary metabolite data from Denmark are shown in Table 41. Exposures calculated from 24

hour samples are based on the urinary metabolite concentration (µmol/l). In the case of exposures

calculated from spot urine samples the urinary metabolite concentration is normalised against

creatinine or urinary volume references in order to estimate the daily excretions.

TABLE 41

ESTIMATED DIN P IN TAKES (µG/KG BW /DAY) BASED ON U RINARY METABOLITE DATA FROM DEN MA RK (ECHA, 201 3)

Country No. of

subjects

Age

(y)

year Intake

µg/kg bw/day

Basis of estimated in take

50th

percentile

95th

percentile

(max)

DK

N=129

25 26 1 4 24 29 1 1

Boy s 6-1 0 1 1-16 1 7-21 Girls 6-1 0 1 1-16 1 7-21

2006-2008

2.04 1 .42 1 .52 1 .93 1 .53 1 .01

9.02 (9.88) 5.26 (5.36) N.R. (3 .63) 1 0.4 (1 1.9) 6.99 (7 .96) N.R. (2.49)

24 hour urine samples Based on urine levels of MiNP, MHiNP, MOiNP and MCiOP intake based on fractions of dose excreted in urine in adult volunteer experiment (Anderson et al. 2011) using child specific model (Koch, 2007; Wittassek et al. 2007)

DK 60 1 8-26 2006 1 .26 3 .48 Spot samples

Based on urine levels of MiNP, MHiNP, MOiNP and MCiOP

Calculation by Kransler et al. (2012)

DK 250 girls 250 boy s

4-9 4-9

2006-7

2.13 2 .25

3 .03 3 .41

Spot samples Based on urine levels of MiNP, MHiNP, MOiNP and MCiOP Fractional urinary excretion values from Anderson et al. (2011) Calculation by Kransler et al. (2012)

N.R. = n ot reported

The estimated median adult exposure in Denmark is around 1 .3 µg/kg bw/day and 95th percentile

intakes estimated at around 3.4 µg/kg bw/day. As shown in Table 41 the estimated exposure results


for DINP indicate a decrease in exposure with an increase in age, assumed to be a result of higher

dust and food intakes combined with lower body weights (ECHA, 2013). Differences in study

approach and methodology result in significant variability between studies and this makes

comparison of the outcome from different EU countries more difficult. According to ECHA (2013),

there are no biomonitoring data for children under three years of age. Due to the restriction of the

use of phthalates in toys, such monitoring data would not reflect exposure from toys and childcare

articles which can be placed in the mouth, but could be indicative of exposure from other sources.

Similar data for estimated DIDP exposure in Denmark have not been identified. Estimations based

on data from other countries indicate a lower intake of DIDP compared to DINP (ECHA, 2013).

In a newly published study with results from human biomonitoring on a European scale, all 17

participating countries analysed 4 human biomarkers including metabolites of some phthalates in

urine. DINP was part of the study. Samples were taken from children aged 6-11 years and their

mothers aged 45 years and under. Results of urinary metabolites of DEP, DINP and DIDP measured

in Danish mother-child pairs are shown in Table 42 (Frederiksen et al., 2013). The results showed

higher levels in children compared to mothers, with the exception of MEP, a metabolite of DEP,

which is not regulated and is mainly used in cosmetics. A possible explanation for the generally

higher levels in children is children’s relatively higher intake: they are more exposed to dust, playing

nearer the ground, and have more frequent hand-to- mouth contact; and they eat more than adults

in relation to their weight. Consumption of convenience food, use of personal care products and

indoor exposure to v inyl floors and wallpaper have all been linked to higher phthalate levels in urine

(DEMOCOPHES, 2013; Frederiksen et al., 2013).

TABLE 42

U N IRARY PHTHALATE METABOLITES IN DANISH MOTHER-CHILD PAIRS (FREDERIKSEN ET AL., 201 3)

Diester

phthalate

Phthalate

metabolite

Limit of

detection

Mother (n=145) Child (n=143)

LOD Mean 50th

percen-

tile

95th

percen-

tile

Mean 50th

percen-

tile

95th

percen-

tile

Concentration (ng/ml)

DEP MEP 0.53 7 4 29 359 28 20 68

DINP MiNP HMiNP MOiNP MCiOP ∑DiNPm

0.61 0.26 0.25 0.11

0.30 5.3 2.9 9.8 24

2 .7 1 .4 6.2 1 3

1 .9 1 9 1 3 35 1 00

0.88 1 23 7 .2 22 58

5.0 2.6 7 .8 20

3 .2 38 1 7 46 1 11

DIDP MiDP 0.69 <LOD <LOD <LOD <LOD <LOD <LOD

Creatine adjusted concentration (µg/g crea)

DEP MEP 64 29 298 28 1 9 93

DINP MiNP HMiNP MOiNP MCiOP ∑DiNPm

0.3 5.1 2 .7 9.9 24

2 .6 1 .3 5.2 1 2

1 .6 1 7 9.9 37 81

0.91 1 4 7 .6 24 61

5.0 2.7 8.2 22

2.7 28 1 4 7 1 02


The study also concludes that the sum of DEHP-metabolites in Danish children participating in the

study was lower than the average adjusted for urinary creatinine, age and gender for the 17 involved

EU countries.

DEP

A recent study has investigated children’s phthalate intakes (DEP, DnBP, DiBP, BBzP and DEHP)

and resultant cumulative exposures estimated from urine compared with estimates from dust

ingestion, inhalation and dermal absorption in their homes and daycare centers. Based on the

results, it was concluded that the exposure to the low-molecular-weight phthalates such as DEP

(and DnBP and DiBP) occurring indoors via dust ingestion, inhalation and dermal absorption can

meaningfully contribute to the total intake of these substances. Dermal absorption and inhalation

appear to be the most important routes of env ironmental exposure for these chemicals. None of the

children had intakes that exceeded the TDI of 500 mg/kg bw for DEP taken from a statement on

dietary exposure to phthalates by the independent Committee on Toxicity of Chemicals in Food,

Consumer Products and Environment in the UK4 (Bekö et al., 2013). The study involved dust

samples collected between March and May 2008 from the homes of 500 children and from the 151

day care centers in a major city in Denmark. Morning urine samples from 441 children were

collected between August 2008 and April 2009.

Sev eral biomarker studies from different parts of the world report on phthalate ester metabolites in

urine and present estimates of daily intake based on these results. In a study estimating the range of

adult intake of DEP based on both the biomarker method and a scenario-based approach (indirect),

and results from USA, Japan, Taiwan and Europe, the daily intake estimated from urinary

metabolites was in the range of 0.77 to 12.3 µg/kg/day with a median value of 5.5 µg/kg/day (Clark

et al., 2011). Most data were retrieved from the US National Health and Nutrition Examination

Survey with data on urinary metabolites obtained from 2001 -2002 (Clark et al., 2011). The adult

daily intakes based on indirect studies were reported at (Clark et al., 2011):

0.007 - 0.13 µg/kg/day from the diet only,

0.051 – 0.46 µg/kg/day from diet, air and dust, and

4.27 µg/kg/day from diet, air, dust and consumer products excluding personal care products

These figures indicate that the major contribution of DEP is from consumer products. It should

however be noted, that most data for individual foods are more than 20 years old. Based on the

biomarker data, intake of DEP is highest in the USA, followed by Germany, Taiwan, and Japan. This

difference between regions is also apparent in the measured concentrations of DEP in indoor air; in

the USA, the average concentration is approximately two times the average concentration in Europe

and six times the average concentration in Japan (Clark et al., 2011).

DEP has been measured in human milk in a study investigating phthalate diesters and their

metabolites in human breast milk, blood or serum, and urine as biomarkers of exposure in

v ulnerable populations in a small study population in Sweden (Högberg et al., 2007). Identified

phthalate diesters and metabolites in milk and blood or serum, were present at concentrations close

to the limit of detection. Most phthalate metabolites were detectable in urine at concentrations

comparable to results from the United States and Germany. No correlations could be established

between urine concentrations and those found in milk or blood/serum for single phthalate

metabolites. Data from the study were comparable with previous results showing comparatively

high concentrations of phthalate metabolites in Finnish and Danish mothers’ milk. The

concentrations of DEP in milk was measured in the range of 0.22 – 1 .45 ng/ml with a mean value of

0.30 ng/ml. It is concluded that concentrations of phthalate metabolites in urine are more

informative than those in milk or serum, but urine metabolite estimates are not suitable to estimate

exposure to phthalates through milk ingestion by breast-fed infants.

4 http://cot.food.gov .uk/

http://cot.food.gov.uk/


DIPP and DPHP

Specific biomonitoring data for DIPP and DPHP have not been identified.

6.4 Hum an health im pact

DEP

The Scientific Committee on Consumer Products (SCCP) has re-evaluated its opinion from 2002 on

the safe use of DEP in cosmetics in 2006 and found no reason to update the opinion. It is concluded

that DEP may be used as fragrance solvent at a maximum concentration of 50% (hypothetical usage

v olume of 1 ml). This results in a potential exposure of 28 mg/day giving a Margin of Safety (MoS)

of 321 or as an ethanol denaturant at a maximum concentration of 1 % (hypothetical u sage volume

of 1 0 ml), resulting in a potential exposure of 5.6 mg/day giving a MoS of 1 607. The worst case MOS

calculation made by the Scientific Committee on Cosmetics Products and Non-Food Products

intended for Consumers (SCCNFP) for all cosmetics was 1 61, assuming 10% of diethyl phthalate in

all cosmetic products (SCCP, 2006).

DINP/DIDP

Risk assessment is carried out for DINP and DIDP in the ECHA review.

The overall conclusions from the ECHA review regarding the risk from DIDP and DINP are as

follows: ECHA concluded that a risk from the mouthing of toys and childcare articles with DINP

and DIDP cannot be excluded if the existing restriction were lifted. No further risks were

identified. These conclusions were supported by ECHA’s Committee for Risk Assessment. Based on

the risk assessment in this report, it can be concluded that there is no evidence that would justify a

re-examination of the existing restriction on DINP and DIDP in toys and childcare articles which

can be placed in the mouth by children (restriction entry 52 in Annex XVII to REACH).

For children the reasonable worst case RCRs ranging from 1.3 to 2.0 indicate a risk of liver

toxicity for children of 0-18 months old from mouthing toys and childcare articles containing

DINP or DIDP. Thus, it is concluded that a risk from the mouthing of toys and childcare articles

with DINP and DIDP cannot be excluded if the existing restriction were lifted (i.e. in the scenario

where DINP or DIDP would be present in toys and childcare articles). This conclusion was

supported by RAC (ECHA 2013a,b).

For adult consumers RCRs of 0.4 in the reasonable worst case use of sex toys, it seems not likely

that the use of sex toys with DINP or DIDP would result in a risk. This conclusion is subject to

substantial uncertainties with regard to exposure duration and migration rates of the phthalates

from sex toys.

Dermal exposure from for instance PVC garments is not anticipated to result in a risk for the

adult population. Exposure from food and the indoor environment are not very significant in the

adult population, which is confirmed by the available biomonitoring data.

Based on the risk assessment in this report, it can be concluded that no further risk management

measures are needed to reduce the exposure of adults to DINP and DIDP.

In the survey and health assessment of the exposure of 2 -year-olds to chemical substances in

consumer products (Danish EPA, 2009) referred to in 6.2.2, the DNEL for DINP was calculated at

1 .6 mg/kg BW/day (NOAEL/AF) based on a NOAEL of 276 mg/kg bw/day for antiandrogenic

effects (reduced testicular weight in mice) and an assessment factor of 1 75. The combined daily

ingestion of DINP from both direct and indirect exposure pathways, including exposure to toys

which are no longer allowed to contain more than 0.05 %(w/w) DINP, resulted in total ingestion

(95th percentile) of 31.23 µg/kg bw/day for the summer scenario and 37.54 µg/kg bw/day for the

winter scenario and risk characterisation ratios (RCRs) of 0.020 and 0 .023 respectively. The


resulting RCRs indicates that DINP does not constitute a risk under the assumptions made in the

report.

In the project on exposure of pregnant consumers to suspected endocrine disruptors (Danish EPA,

2012) referred to in 6.2.2 the DNELAA (for substances mainly with antiandrogenic effect) of 1 500

μg/kg bw/day based on a NOAEL of 300 mg/kg bw/day in a study showing reduced semen quality

and increased nipple retention in male rats exposed during pregnancy and lactation was used to

calculate a risk characterisation ratio of 0.0015. The resulting RCR indicated that DINP does not

constitute a risk under the assumptions made.

No risk assessments have been identified for DIPP, DMEP and DPHP.

Combined risk assessment

The Danish EPA has used the concept of dose addition in a cumulative risk assessment in relation to

the proposal for restrictions on four phthalates (Annex VX dossiers for DEHP, DBP, BBP, and

DIBP) in 2012, and in relation to risk assessment of the total exposure of two-year-olds to chemical

substances (Danish EPA, 2009) and in other projects addressing risk to v ulnerable groups such as

pregnant women. A study by Christen et al. (2012) demonstrates that concentration addition is an

appropriate concept to account for mixture effects of antiandrogenic phthalates.

On the other hand, in the case of possible combination effects from exposure to e.g. anti-androgens

and estrogens simultaneously, there is not sufficient information available.

The ECHA review of DINP and DIDP addresses the need for considering combined effects of

phthalates with same mode of action in the risk assessment of the substances: Based on the

available information from in vitro studies, different phthalates seem to exhibit various effects –

stimulatory, inhibitory or no effects – on certain endocrine parameters. Phthalates having the

same mode of action or the same adverse outcome are likely candidates for combined risk

assessment. However, the mode of action should always be carefully considered in selecting

candidates for combined risk assessment.

DINP has anti-androgenic properties and it could be appropriate to include this substance in a

combined risk assessment of phthalates with anti-androgenic properties. DIDP, on the other hand,

does not have similar properties/potency and it would not be justified to group DIDP in a combined

risk assessment of phthalates on the basis of anti-androgenic properties.

There seem to be sufficient grounds to assess combined effects of DINP and DIDP (as well as DEHP

and possibly other substances) on the basis of liv er toxicity (spongiosis hepatis) (ECHA, 2013).

Cumulative risk assessment should also be considered in relation to the other selected phthalates.

Although they are not all equivalent in terms of sev erity of their effects, e.g. the ability to cause

adv erse effects on the development of the male reproductive system should be considered.


DIPP and DMEP are subject to harmonised health classification and both substances are classified

for reproductive toxicity in Category 1 B. The four other phthalates selected for the study are self-

classified by industry. No classification is suggested for DPHP and although much data is available

for DEP, DINP, and DIDP, only few of the notifiers have self-classified these substances. The

reasons provided by the notifiers not suggesting a classification of the substances are typically "data

lacking" and "conclusive but not sufficient for classification". Denmark will in 2013 assess whether

there is sufficient evidence of endocrine disrupting effects of DINP to prov ide a basis to support a

harmonised classification or other measures.


The six phthalates are generally of low acute toxicity via all routes and with low the skin and eye

irritation potential. There are case reports referring to skin sensitisation to plastic articles in

patients with dermatitis, e.g. in relation to DEP, but in general phthalates are not considered

sensitising. The main reason for concern in relation to phthalates and health hazards are adverse

effects on the reproductive system of in particular male animals and endocrine disruption. Of the

selected phthalates DEP has been evaluated against the proposed Danish criteria for endocrine

disrupters as a suspected endocrine disrupter in category 2a.

No significant exposure to DMEP is expected as the substance is not registered for use in the EU.

DEP has not been identified as an ingredient in cosmetic and personal care products in Denmark

but may be imported from other countries.

Occupational exposure is primarily expected via dermal contact in relation to handling of flexible

PVC products, formulation and use of sealants and paints, and contact with cosmetics and personal

care products. Direct consumer exposure is expected from dermal contact with various flexible PVC

products, wires and cables and in particular imported cosmetics and personal care products.

Indirect exposure of consumers occurs in relation ingestion of food, and inhalation and ingestion of

dust in the indoor climate.

In a newly published study with results from human biomonitoring on a European scale, all 17

participating countries analysed among others metabolites of DEP, DINP and DIDP, in urine.

Samples were taken from children aged 6-11 years and their mothers aged 45 years and under. The

results showed higher levels in children compared to mothers, with the exception of MEP, a

metabolite of DEP, which is not regulated and is mainly used in cosmetics. A possible explanation is

children’s relatively higher intake: they are more exposed to dust, playing nearer the ground, and

have more frequent hand-to- mouth contact; and they eat more than adults in relation to their

weight. Consumption of convenience food, use of personal care products and indoor exposure to

v inyl floors and wallpaper have all been linked to higher phthalate levels in urine.

DINP and DIDP have been reviewed by ECHA in relation to entry 52 in Annex XVII to REACH. It

was concluded that a risk from the mouthing of toy s and childcare articles with DINP and DIDP

cannot be excluded if the existing restriction were lifted. No further risks were identified. These

conclusions were supported by ECHA’s Committee for Risk Assessment.

The ECHA review also addressed the need for considering combined effects of phthalates with same

mode of action in the risk assessment of the substances. This is relevant e.g. in relation to

antiandrogenic properties of DINP and in relation to liver toxicity (spongiosis hepatis) for DINP

and DIDP but should be considered in genetal for substances with same endpoint and mode of

action.

Data gaps

Data gaps or areas where an improved understanding would be u seful are identified as follows

based on the reviewed literature:

Identification of the most important metabolites to be used as a biomarker for human

exposures

Further research addressing the cumulative exposure to multiple phthalates and other

antiandrogenic and estrogenic substances seem to be warranted

Limited information on endocrine specific end-points for some phthalates

Better understanding of combination effects of antiandrogens at different levels


7. Information on alternatives

7 .1 Alternatives to DINP, DIDP and DPHP use in PVC

Alternatives to the phthalates in flexible PVC can be grouped into two types:

Alternative plasticisers for flexible PVC

Alternative plastics with similar properties as flexible PVC.

Here, we primarily deal with alternative plasticisers, as they require the least adaption efforts by

industry.

7 .2 General features of plasticisers relevant in substitution efforts






supported by a large number of measuring methods designed for this purpose.

To get an impression of the many possibilities for plasticising polymers, it has therefore been

chosen to present extracts from an introduction given by Maag et al. (2010) to the basic functions of

plasticisers:

“We describe here the basics of external plasticisation of PVC, the major use of plasticisers. The

word "external" denotes plasticisers that are not bound chemically in the polymer matrix, and can

therefore migrate out of the polymer at certain conditions. Polymers can also be plasticised

"internally" by incorporation of functional groups into the polymer itself, which imparts

flexibility. Phthalates are external plasticisers, as are their direct substitutes, and external

plasticisation is described in this section.

PVC consists of long chains of the basic vinyl building block. The polymer is bound together in

three dimensions by two overall types of forces. In some points the polymer is crystallised into a

fixed geometric pattern with strong chemical bonds. In the rest of the polymer matrix, the

polymer chains are somewhat more randomly organised and bound together by weaker forces

based on attraction between polar parts of the polymer chain with different polarity. The ideal

plasticiser works in these less strictly organised parts of the polymer.

In the hard polymer, the chains are packed closely together, also in the randomly organised parts,

and the weak attraction forces bind the polymer together to a rigid structure with no flexibility.

The (external) plasticiser has solvent capabilities and penetrates the less strongly bound parts of

the polymer in the so-called swelling, where plasticiser and polymer resin is mixed. In the

polymer, the plasticiser acts as a kind of sophisticated lubricant, as it creates distance between the

freely organised polymer chain parts, and shields the attraction forces between polar parts of the

chain, and thereby weakens the attraction between the chain parts. This allows for more free

movement amongst the weakly bound chain parts, which means that the material becomes

flexible.


The properties of the plasticiser have immense influence of how well it plasticises the polymer, and

on the performance characteristics of the plasticised material. I t is however important to

understand that the plasticiser (with a few exceptions) does not form specific chemical bonds with

the polymer, and there is therefore in principle a flexibility in which type and configuration of

plasticisers that actually can be used to obtain the desired plasticising performance

characteristics.

External plasticisers may be separated from the PVC matrix due to extraction by solvents, oils,

water, surface rubbing, volatility, migration into adjacent media, or degradation mechanisms. ”

The key functional characteristics involved in plasticiser selection include:

Solv ency in the polymer resin (also called compatibility or miscibility)

Efficiency (defined as the flexibility it gives in the polymer compared to DEHP)

Volatility

Diffusivity

Low temperature performance

Structure of some plasticiser families


functionalities in common with the phthalates family. This can be seen in Figure 3 , which shows

representatives of some different plasticiser families, of which several are relevant as plasticiser

alternatives to the phthalates dealt with in this report. They are typically branched, quite



Many similar plasticisers have however distinctly different impacts on health and environment, and

are therefore relevant alternatives to phthalates. This is probably primarily due to the fact that

many types of interactions with biological systems are substance specific, and even structure-

specific meaning that substances with identical chemical composition may work differently, if just a

part of the molecule has shifted position from one place to another (as the case is for DEHP and

DEHT).

The substance family of the plasticiser influences its performance significantly, but some functional

groups in the molecules also influence the performance across families, and plasticisers can

therefore to a certain extent be tailor-made to suit different performance needs. In addition,

plasticisers can be mixed to achieve desired properties. For more information on the defining

characteristics of plasticisers, see Maag et al. (2010).

FIGURE 3

CHEMICAL STRU CTU RE OF REPRESEN TATIVES OF DIFFEREN T PLASTICISER FAMILIES (FROM MAA G ET AL. 201 0).

Ortho-phthalates (Example:

DEHP, DOP; di 2-

ethylhexylphthalat)

Terephthalates, (Example:

DEHT, DOT DOTP; di 2-

ethylhexyl terephthalate)


Tr imellitates (Example:

TOTM; tri (2-ethylhexyl)

tr imellitate)

A liphatic dibasic esters,

a dipates (Example: DEHA,

DOA = di (2-ethylhexyl)

a dipate )

(DBS = Dibutyl sebacate)

Ben zoates (Example: DGD;

dipropylene glycol

dibenzoate)

Citrates (Example: ATBC;

a cetyl tributyl citrate)

Ph osphates (Example: tri(2-

ethylhexyl) phosphate)

Gly ceryl triacetate (GTA,

Tr iacetin)

7 .3 Possible plasticiser alternatives to DINP, DIDP and DPHP in PVC

According to ECPI (2013), DPHP is often used as a phthalate alternative to DIDP because only

minor compound changes are needed to adapt wire formulations for example to DPHP. It also

matches DIDP performance in automotive applications.


It has not been possible to identify any studies specifically focussing on alternatives to DINP, DIDP

and DPHP. Most av ailable information on alternatives to primary plasticisers like DINP, DIDP and

DPHP has therefore been reviewed based on results from the search for substitutes for the classic

general plasticiser DEHP (to which DINP and to as lesser extend DIDP and DPHP are the key

alternatives today).

Sev eral studies of alternatives to the classified phthalates DEHP, DBP and BBP have been

undertaken and some studies lists the DINP and DIDP together with other alternatives to the

classified phthalates while other of the studies focus on non -phthalate alternatives. From the

studies which include both DINP and DIDP and n on-phthalate alternatives it is possible to extract

some information which can indicate to what extent the non -phthalate alternatives can be

considered alternatives to DINP, DIDP and DPHP. A closer analysis would however be needed as

the properties of DINP, DIDP and DPHP are not exactly the same as those of DEHP. DINP, DIDP

and DPHP are more expensive that DEHP, but also have some advantages for some applications,

and experience with substitution of non-phthalate alternatives for DEHP does not necessary imply

that the substances can substitute for DINP, DIDP and DPHP without research and development

and changes in process conditions and machinery.

Maag et al. (2010) focus in a study for the Danish EPA on non -ortho-phthalate alternatives to

DEHP, DBP and BBP. Based on information on the plasticisers found in toys and childcare articles

and initial information from manufacturers, a gross list of 25 potential non -phthalate alternatives

was compiled and from this list 10 plasticisers were selected for further assessment.

The study included a survey of plasticisers applied in toys and childcare products with restriction on

the use of DINP and DIDP. Three of the non-ortho-phthalate plasticisers were found in a significant

percentage of surveys of phthalates in toys and are reported by all responding Danish

manufacturers of toy s as used as alternatives to phthalates: DINCH, DEHT and ATBC. All three are

marketed as general plasticiser alternatives to DEHP. Among the non -phthalate plasticisers, only

DEHT may candidate to be a one-to-one substitution for all traditional applications of DEHP, but

not necessarily for DINP, DIDP and DPHP. Which substitutes are suitable depends on the actual

processing conditions and the desired properties of the final product. Finding the right plasticiser

for a giv en application is often a complex process, as described above. Many technical criteria have

to be met simultaneously and comprehensive testing of the performance of the polymer/plasticiser

sy stem is often required. By way of example one Danish manufacturer reported that the

dev elopment led to the use of a mixture of ATBC, DINCH and DEHT, which could be blended in a

v ariety of combinations to achieve softened PVC that performed to the required standards with the

existing production setup (Maag et al, 2010).

A summary of the findings of the study is shown in Table 43 below. The price of the alternatives is

indicated as compared with DEHP. The price of DINP and DIDP is approximately 15% higher than

the price of DEHP. Similar price data has not been found for DPHP.

TABLE 43

SU MMARY OF THE TECHN ICAL ASSESSMEN T OF A LTERNATIVE PLASTICISERS (IN ALPHABETICAL ORDER), AN D

THEIR PRICES RELATIV E TO DEHP (MAAG ET AL., 201 0)

Abbreviation Su bst a nce na m e CA S No Ov era ll t ech nica l a ssessm ent Price

rela t iv e t o

DEHP *1

A SE

Su lfonic acids, C10 – C18-

a lkane, phenylesters

9 1082-17-6 A SE is a general plasticiser alternative to

DEHP. The producer has indicated significant

m arket experience for most traditional DEHP,

DBP a n d BBP uses.

+



rela t iv e t o

DEHP *1

A TBC

A cetyl tributyl citrate 7 7 -90-7 Th e performance of ATBC on some parameters

seems similar to DEHP, indicating technical

su itability for substitution of DEHP for some

a pplications. The higher extractability in

a queous solutions and the higher volatility

m ay reduce the performance of ATBC as a

pla sticiser in PVC. The data available does not

a llow a closer assessment of ATBC's technical

su itability as alternative to DEHP, DBP and

BBP

++

Mixture of

benzoates

incl. DEGD

Ben zoflex 2088 Mix of 120-55-8, 27138-31-4, 120-56-9

Th e producer has indicated significant market

ex perience in several of the traditional DBP

a n d BBP specialty plasticiser applications and

certain DEHP applications, notably in the non-

poly mer (adhesives, sealants, etc.) and PVC

spr ead coating (plastisol) application fields.

A ccording to the producer, Benzoflex 2088

(w ith DEGD) has become the main non-

ph thalate alternative to DBP or BBP in vinyl

flooring production in Europe. The higher

ex tractability in water may limit its use for

som e applications.

≈

COMGHA Mix ture of 12-(Acetoxy)-

stearic acid, 2,3-

bis(acetoxy)propyl ester

a n d octadecanoic acid,

2 ,3-(bis(acetoxy)propyl

ester

Mix of 330198-

9 1-9 and 33599-

07 -4

A ccording to the producer, COMGHA still has

r elative moderate market experience, albeit

w ith many examples of full scale usage and

pilot/lab scale tests, and significant market

ex perience in some plastisol application and

cosmetics. The producer found good

per formance on key technical parameters

in dicating a potential for substituting for

DEHP and perhaps for DBP and BBP in some

traditional uses of these substances.

++

DEHT

Di (2 -ethyl-hexyl)

terephthalate

6 422-86-2 DEHT is a general plasticiser alternative to

DEHP. Today, terephthalates like DEHT are

m ore commonly used in the USA than in

Eu rope.

≈

DINA

Diisononyl adipate 3 3703-08-1 DINA has mostly been used for low

temperature PVC applications and in PVC

film/wrapping . The data available for this

study does not allow clear-cut conclusions as

r egards DINA's suitability as alternative to

DEHP

+



rela t iv e t o

DEHP *1

DINCH

Di-isononyl-cyclohexane-

1 ,2dicarboxylate

1 66412-7 8-8 Th e producer’s sales appraisal indicates a

r elatively wide usage of DINCH for general

pla sticiser purposes. DINCH was the most

fr equently found plasticiser in two European

su rveys of plasticisers in toys and childcare

a rticles. The data available does not allow a

closer assessment of DINCH's technical

su itability as alternative to DEHP, DBP and

BBP.

+

DGD

Dipr opylene glycol

dibenzoate

27 138-31-4 Th e fact that DGD for many years has been a

w ell known and much used competitor to BBP,

especially in PVC flooring and in PVA

a dhesives, indicates a clear potential for

su bstituting DGD for BBP, from a technical

point of view. DGD may probably also

su bstitute for some traditional uses of DEHP

a n d DBP.

≈

GT A

Gly cerol Triacetate 1 02-76-1 A ccording to a producer, GTA can substitute

for DBP and BBP in adhesives, inks and

coa tings. The data available does not allow a

closer assessment of GTA's technical suitability

a s a lternative to DEHP, DBP and BBP.

+

T XIB Tr imethyl pentanyl

diisobutyrate

6 846-50-0 TXIB was found in more than 10% of the

samples in surveys of plasticisers in toys and

ch ildcare articles. However, the producer does

n ot consider TXIB an alternative to DEHP,

DBP or BBP, and the usage of TXIB in vinyl

flooring has declined in the 1990’s due to high

em issions from end products. Consequently,

TXIB seems not to be a suitable alternative to

DEHP, DBP or BBP.

NA

*1 Ba sed on comparison with DEHP, but DBP and BBP are reported to have similar price and the notation

th erefore serves as indicating price relative to DBP and BBP as well. The price of DINP and DIDP is

a pproximately 15% higher than the price of DEHP. "≈" means similar price or slightly lower or higher than

DEHP; "+" m eans somewhat higher price (10-50% higher) than DEHP and "++" means significantly higher

pr ice than DEHP. The report provides actual price examples.

In a study on cost curves of reducing the use of DEHP, BBP and DBP for the European Chemicals

Agency (ECHA) Lassen et al. (2013) have indicated the costs of the replacement of the three

phthalates with DINP, DIDP and a number of non -phthalate alternatives.

As shown in Table 44, the effective price of the non-ortho-phthalate alternative DEHT was in the

same price range as the price of DINP and DIDP, whereas ASE and DINCH were somewhat more

expensive. It is in general very difficult to obtain precise information on the prices of the plasticisers

and this information is considered confidential.


The effective price difference depends on the price of the alternative and a substitution factor (also

called “efficiency”), which indicates the amount of the a lternatives needed as compared with DEHP

in order to obtain the same plasticising properties. According to Lanxess (as cited by Lassen et al.,

2013), the substitution factors may typically vary by less than ±5% for the most used direct

alternatives to DEHP. The factor varies with the specific processing conditions, but it is not possible

to indicate some general differences between the different processing types (e.g. plastisol processing

v s. calendering).

The content of DEHP in plasticised PVC varies with the application but is typically in the range of

20-40% of the plastics and an increase in the price of the plasticiser of e.g. 30% will result in a

material price increase of 1 0% for the plastic material.

Prices of chemicals (and other industrial products) tend to decrease as production capacity and

competition is increased. Different chemicals are however based on different raw materials and

more or less complex and resource demanding chemical synthesis technologies. This of course sets

limits to the minimum prices attainable even in a mature market, and some of the alternative

plasticisers described may remain at higher price levels.

Besides the price of the plasticisers, the substitution of the phthalates may imply some costs of

research and development for reformulation and process changes which is discussed further below.

TABLE 44

PRICE OF ALTERN ATIVES AS COMPARED WITH DEHP FOR U SE IN PVC (LASSEN ET AL., 201 3)

A lternative CA S No Price

com pared t o

DEHP

Su bstitution

fa ct or, %

Effect iv e

price

com pared t o

DEHP

Sou rce of

inform a t ion

DINP (Jayflex™

DINP)

6 8515-48-0 +13-16% u p to 106 *1 +13-20% Ex x onMobil,

m anufacturer of

a lternative / ICIS

pr icing

DIDP (Jayflex™

DIDP)

6 8515-49-1 +13-16% u p to 110 *1 +13-24% -“ -

DINP 6 8515-48-0 +5 % 1 07 +12% DSU, extrusion and

in jection moulding

PV C

DINP 6 8515-48-0 +15% 1 06 +1 8% DSU, extrusion PVC

DIDP 6 8515-49-1 +5 % 110 +16% -“ -

Hexamoll® DINCH

Di-isononyl-

cy clohexane-1,2-

dicarboxylate,

1 66412-7 8-8 +5 0% 1 07 + 6 1% -“ -

DEHT , DOTP

Di(2-ethylhexyl)

t erephthalate

6 422-86-2 +1 0% 1 07 +1 8% -“ -

DEHT , DOTP

1,4- Di(2-ethylhexyl)

t erephthalate

6 422-86-2 +15% 1 00-103 +15-18% Ea stman,

m anufacturer of

a lternative


A lternative CA S No Price

com pared t o

DEHP

Su bstitution

fa ct or, %

Effect iv e

price

com pared t o

DEHP

Sou rce of

inform a t ion

Citroflex® A-4

A cetyl Tributyl

Citrate,

7 7 -90-7 +5 0-100% 1 00 +5 0-100% V ertellus,

m anufacturer of

a lternative

Citroflex®

n -Butyryltri-n-hexyl

citrate

8 2469-7 9-2 +>5 0-100% n ot indicated +>5 0-100% V ertellus,

m anufacturer of

a lternative

Mesamoll® (ASE)

Su lfonic acids, C10 –

C18-a lkane,

ph enylesters,

7 0775-94-9 n ot indicated

[+7 5% *2]

n ot indicated n ot indicated La nxess,

m anufacturer of

a lternative

Unimoll AGF®

Mu lti-constituente

su bstance - mixture of

a cylated glycerides,

m ixture n ot indicated n ot indicated n ot indicated -“ -

DOA

Di-2-ethylhexyl

a dipate, Adimoll® DO

1 03-23-1 *3 9 5 *3 -“ -

ODS

n -Octyl n-decyl

su ccinate mixture,

Uniplex® LXS TP

ODS)

m ixture *3 1 00 *3 -“ -

BEHS

Benzyl-2ethylhexyl

su ccinate mixture,

Uniplex® LXS TP

BEHS

m ixture *3 9 5 *3 -“ -

*1 Th e substitution factor depends on the concentration of phthalates in the material. The 106% and 110%

r epresent the typical situation e.g. in cable, film and sheet, but it may be less for some applications.

*2 Pr ice difference indicated by Maag et al., 2009.

*3 Pr ice reported, but considered confidential.

The experience with substitution of DEHP by product group, as reported by the manufacturers of

the alternatives, is shown in Table 45. As indicated in the note to the table, the manufacturer of

DEHT, Eastman has indicated that DEHT has more typically been used for substitution of DINP,

and DEHT can technically replace both DEHP and DINP in all flexible PVC products. DEHP is

widely used in the USA for the same applications as DINP is applied in Europe. Eastman indicates

that DEHT is a drop-in alternative for DEHP for most applications and no significant costs of R&D

and process changes are foreseen (Lassen et al., 2013). The same is probably the situation as

concern substitution of DEHT for DINP.

Lanxess indicates according to Lassen et al. (2013) that they believe that ASE and DOA can replace

DEHP without any changes to the existing equipment. Additional costs may be incurred by minor

one-off reformulating work, the costs of this is indicated as “insignificant” by the manufacturer. The


company has indicated that the main part of the R&D will take place by the manufacturer of the

alternatives in order to ensure that the plasticiser blend has the desired properties.

TABLE 45

EXPERIEN CE W ITH SU BSTITUTION OF DEHP BY PRODUCT GROUP AS REPORTED BY THE MANUFACTURERS; SEE

DEFIN ITION OF SCORES U SED IN N OTES (LASSEN ET AL., 201 3)

A pplication DINP DIDP DEHT /

DOT P *2

Citroflex

® A -4

A SE DOA ODS

Exxon Mobil Ea st m a n V ertellus La nxess

Ca lendering of film, sheet and

coa ted products *1

1 1 3 2 2

Ca lendering of flooring and

roofing *1

1 1 4 4

Ext rusion of hose and profile *1 1 1 3 2 2

Ext rusion of wire and cable 1 1 3 2 2

Ext rusion of miscellaneous

products from compounds

1 1 2 2 2

Injection moulding of footwear

a nd miscellaneous

1 1 ? 2

Slu sh/rotational moulding *1 1 ?

Spread coating of flooring *1 1 2

Spread coating of coated fabric,

wa ll covering, coil coating, etc. *1

1 1 1 2 2 4

Ca r undercoating *1 1 1 2 4

Non -PVC polymer applications

(a crylics)

1 2 ? 2

A dhesives/sealant (e.g. PU),

ru bber

1 2 2 2 1

La cquers and paint 2 2 2

Printing ink 1 2 2 1

Notation used: 1) main alternative on market; 2) Significant market experience, 3) Some examples of full scale

ex perience, 4) Pilot/lab scale experience

*1 A ccording to ExxonMobil, DEHP is no longer used in most of those end-uses but has been replaced by high

ph thalates (DINP and DIDP). However this may not be true when considering the use of DEHP in Eastern

Eu rope.

*2 Th e manufacturer Eastman has indicated for this study a relatively small number of applications where they

h ave experience in substituting DEHT for DEHP. According to the company, DEHT has more typically been

u sed for substitution of DINP and DEHT can technically replace both DEHP and DINP in all flexible PVC

pr oducts.

Costs of Research and Development

According to (Lassen et al., 2013) some adjustment is often necessary when replacing the

plasticisers and this is typically done in cooperation between the manufacturer and the downstream

user, but the one-of costs of research and development (R&D) and investments in equipment is

generally low compared to the costs of the plasticisers. Particular high costs of research and


dev elopment is expected for layered flooring, because of its technical complexity. In the models of

Lassen et al. (2013) it is assumed that the costs of R&D for per manufacturing site is 300,000 €

while it for other applications areas is 60,000 €.

7 .4 Alternatives to DEP, DMEP and DIPP

Information on specific alternatives to DEP, DMEP and DIPP has been searched for on the Internet

in this study, but aggregated information was scarce.

As mentioned in Section 3 .3, a survey of 23 nail polishes/lacquers marketed in California in 2012

(focusing on DBP, toluene and formaldehyde), found no DEP with the analysis methods used, but

DBP in 9 products and no DBP but other plasticisers in other 9 products. In 5 products, no

plasticisers were observed with the use analytical methods. The other plasticisers observed were

camphor (mentioned as a secondary plasticiser as well as a fragrance), dioctyl adipate, tributyl

phosphate, butyl citrate, triphenyl phosphate, N-ethyl-o-toluene sulfonamide, N-ethyl-p-toluene

sulphonamide, P-toluene sulphonamide (tosylamide) (California EPA, 2012).

As regards denaturing of alcohol, a former DEP use in the EU, Regulation 162/2013 lists the

following substances as allowed denaturants (of which most are only allowed in certain countries

specified in the regulation); it should be noted that several of them have substantial adverse effects

on human health or the environment. The denaturing mixture prescribed for all Member States

without national rules is based on the three substances isopropyl alcohol (IPA), methyl ethyl ketone

(MEK) and denatonium benzoate. DEP must thereby be considered as obsolete as a denaturant in

the EU and with many actual alternatives available. It has not been possible to ev aluate the

env ironment and health characteristics of these substances within the framework of this review.

TABLE 46

DEN ATU RANTS LISTED IN EU REGULATION 162/201 3 OF 21 FEBRUARY 201 3

Su bstance name CA S no.

A cetone 67 -64-1

CI reactive red 24 7 0210-20-7

Crude pyridine n ot available

Crystal violet (C.I. No 42555) 5 48-62-9

Denatonium benzoate 37 34-33-6

Et hanol 6 4-17-5

Et hyl acetate 1 41-7 8-6

Et hyl sec-amyl ketone 5 41-85-5

Et hyl tert-butyl ether 6 37-92-3

Fluorescein 2 321-07-5

Formaldehyde 5 0-00-0

Fu sel oil 8 013-75-0

Ga soline (including unleaded gasoline) 8 6290-81-5

Isopropyl alcohol (IPA) 67 -63-0

Kerosene 8 008-20-6

La mp oil 6 4742-47-8 to 64742-48-9


Su bstance name CA S no.

Met hanol 67 -56-1

Met hyl ethyl ketone (butanone) (MEK) 7 8-93-3

Met hyl isobutyl ketone 1 08-10-1

Met hyl isopropyl ketone 5 63-80-4

Met hyl violet 8 004-87-3

Met hylene blue 6 1-73-4

Mineral naphtha n ot available

Solvent naphtha 8 030-30-6

Py ridine (or Pyridine bases) 110-86-1

Spirit of turpentine 8 006-64-2

T echnical petrol 9 2045-57-3

t ert-butyl alcohol 7 5-65-0

T hiophene 110-02-1

T hymol blue 7 6-61-9

Wood naphtha n ot available

Maag et al. (2010) list the non-ortho-phthalate plasticisers/solvents shown in Table 47 as usable in

traditional applications of these substances. While plasticiser (and solvent) use may be very specific

to the polymer and application in question, the information summarised here indicates however

that there may be technically viable alternatives to DEP, DMEP and DIPP av ailable.

As regards base oils for fragrances, a DEP application, a quick Internet search of the market

indicates that many options are available, including also natural oils like avocado oil , almond oil,

etc.

TABLE 47

N ON -ORTHO-PHTHALATE PLASTICISERS USABLE IN TRADITION AL DEP, DMEP AN D DIPP APPLICATION S (BASED ON

MAAG ET AL, 201 0).

A pplication A lterna t iv e

su bsta nce *1

Remarks on the alterna t iv e’s a pplica t ion (if

a ny )

DEP a pplications

Cosmetics COMGHA A n on-phthalate substitute for general plasticisers in

sen sitive applications. Indicated as used for cosmetics.

DINCH Used in cosmetics (e.g. nail polish).

GTA GTA has a variety of applications including as a

pla sticizer for cigarette filters and cellulose nitrate,

solv ent for the manufacture of celluloid, photographic

films, fungicide in cosmetics, fixative in perfumery,

su pport for flavourings and essences in the food

in dustry, component in binders for solid rocket fuels

a n d a general purpose food additive.


A pplication A lterna t iv e

su bsta nce *1

Remarks on the alterna t iv e’s a pplica t ion (if

a ny )

A TBC

A cetyl tributyl citrate is used in inks, hair sprays and

a erosol bandages.

Pa ckaging film DINA DINA has mostly been used for low temperature PVC

a pplications and in PVC film/wrapping.

A TBC A TBC is widely used in food contact polymers.

DMEP a pplications

Nitrocellulose GTA A ccording to the producer, GTA is used as a plasticizer

for cellulosic resins and is compatible in all proportions

w ith cellulose acetate, nitrocellulose, and ethyl

cellulose. GTA is useful for imparting plasticity and flow

to laminating resins, particularly at low temperatures,

a n d is also used as a plasticizer for vinylidene polymers

a n d copolymers. It serves as an ingredient in inks for

pr inting on plastics, and as a plasticizer in nail polish.

GTA is approved by the FDA for food packaging and

m any other food-contact applications.

A TBC In dicated as used for nitrocellulose paints.

DGD DGD is a high solvating plasticizer that has been used

for many years in a wide variety of applications.

In dicated as used for nitrocellulose.

A SE Good gelling capacity with a large number of polymers.

In dicated as used for nitrocellulose paints.

“ Benzoflex

2 088”

A ccording to the manufacturer this is a high solvating

pla sticizer primarily known for its use in polyvinyl

a cetate, water-based adhesive sy stems and PVC

flooring. Indicated as also used for nitrocellulose paints.

Cellulose acetate, vinylidene

poly mers

GTA See above

Polyvinyl acetate DEGD A ccording to the manufacturer a high solvating

pla sticizer primarily for polyvinyl acetate and water-

ba sed adhesive systems.

Pest icide inerts A TBC In dustrial uses include children’s toys; animal ear tags;

in k formulations; adhesives; pesticide inerts.

DIPP a pplications

Ex plosives and propellant

(ammunition charge)

A TBC A ccording to manufacturer: Cellulosics: Nitrocellulose-

ba sed explosives/ propellants.

Note: *1: See chemical names and CAS numbers in table below.

Environment and health assessment of alternatives

A summary of the inherent properties for the alternative plasticisers investigated by Maag et al.

(2010) is shown in


Table 48 using key parameters: acute and local effects, sensitisation, carcinogenicity, mutagenicity,

reproductive toxicity, persistence, bioaccumulation and aquatic toxicity. Maag et al. concludes as

follows:

"From the overview it can be seen that all ten substances are expected to have low acute toxicity

based on animal studies. With regard to local effects most substances are non-irritating to skin

and eyes or only produce slight irritation which would not lead to classification. None of the tested

substances are sensitising.

Effects from repeated dose toxicity studies mainly include reduced body weight gain, increased

organ weights (liver and/or kidney) and for some substance also changes in clinical chemistry or

clinical pathology parameters. However, more serious pathological effects were not observed.

Studies to evaluate the potential for reproductive/developmental toxicity primarily show toxic

effects on parents and offspring. For TXIB statistically significant reproductive and

developmental toxicity is observed.

Carcinogenicity has only been evaluated for three substances in combined studies. For all three

substances the outcome was negative (no carcinogenicity effect). However, the studies cannot be

considered sufficient to exclude possible carcinogenic effects.

The assessment in this study of the toxic properties of ATCB, COMGHA, DINCH and DEHT is in

line with the recent assessment from the Scientific Committee on Emerging and Newly-Identified

Health Risks (SCENIHR).

All substances have been tested for acute toxicity for at least one exposure route, sensitisation

(except ASE), subchronic toxicity and mutagenicity. All substances except ASE, COMGHA and

DINA have been tested for both reproductive and developmental toxicity.

With regard to carcinogenicity only ATBC, DEHT and DINCH have been tested in combine d

chronic toxicity and carcinogenicity studies. For DEGD, DGD and DEHT estrogenic activity has

been tested in a uterotrophic assay without positive response.

Most data used for the evaluation are considered of good quality, i.e. studies following accepte d

guidelines (OECD or US EPA) or studies considered acceptable at the time they were carried out.

For some of the studies little information is available to evaluate the quality. However, key

information is obtained from IUCLID data sheets, USEPA or OECD HPV robust summaries.).

With regard to environmental properties, none of the 10 studied alternatives meet the criteria for

being a PBT or vPvB substance, although all substances except GTA show one or two of these

properties. GTA (triacetin) appears to be easily biodegradable, it does not bioaccumulate and has

very moderate toxicity in the aquatic environment.

DEGD, DGD and DINA also come out rather favourable, while ATBC and COMGHA come out

negatively despite their degradability because of their aquatic toxicities and bioaccumulative

properties. ASE and DINCH both have low acute toxicities to aquatic organisms, but are not easily

degradable and have high log KOW values. DEHT is also not easily biodegradable and is

bioaccumulative but its aquatic toxicity cannot be fully evaluated based on the data available.

Useful fate data regarding biodegradability (in water) and bioaccumulative properties (either as

BCF or log KOW) are available for all alternatives while other fate data are incomplete for some

substances. With regard to ecotoxicological effect data, results from short-term tests with the

base-set of organisms - fish, crustaceans and algae - exist for all 10 substances although the

duration of some studies deviate from the current OECD standard.


Overall, the data identified are of good quality i.e. they are mostly based on studies performed

according to accepted guideline procedures, and the studies have been evaluated to be reliable

without restrictions or reliable with restrictions (e.g. in the USEPA HPV robust summaries)."


TABLE 48

OVERVIEW OF MAIN TOXICOLOGICAL AND ECOTOXICOLOGICAL PROPERTIES OF POTENTIAL ALTERNATIVES

N

am

e o

f s

ub

sta

nc

e

CA

S N

o.

Hea lt h Env iron m ent

Da

ta q

ua

lity

/

da

ta c

om

ple

ten

es

s

(CM

R a

nd

PB

T)

Ac

ute

, lo

ca

l a

nd

se

ns.

eff

ec

ts

(A/L

/S)

Ca

rc

ino

ge

nic

(C

)

Mu

tag

en

ic (

M)

Re

pr

o-t

ox

ic (

R)

Su

bc

hr

on

ic t

ox

icit

y

Pe

rs

iste

nc

e

Bio

ac

cu

mu

lati

on

Aq

ua

tic

To

xic

ity

*1 *2 *3 *4

A SE 9 1082-17-6 ○/○/○ - ○ ○ ●

●

(n ot readily)

●

Pow ○ 2 / 2

A TBC 7 7 -90-7 ○/(○)/○

○

○ ○ [●] ○

●

BCF ● 1 / 2

COMGHA 3 30198-91-9 ○/○/○ - ○ - (●) ○

●

Pow ● 1 / 2

DEGD 1 20-55-8 ○/(○)/○ - ○ (●) ● ○

(○)

BCF ● 1 / 2

DGD 27 138-31-4 ○/(○)/○ - ○ (●) ● ○

●

Pow ● 1 / 2

DEHT / DOPT 6 422-86-2 ○/(○)/○

○

○ ○ ●

●

(inherently)

●

Pow (●) 1 / 2

DINA 3 3703-08-1

○/○/○ - ○

- ● ○

(●)

(conflictin

g )

○ 1 / 2

DINCH 1 66412-7 8-8 ○/(○)/○

○

○ ○ ●

●

(n ot readily)

●

Pow ○ 1 / 2

GT A 1 02-76-1 ○/○/○ - ○ ○ ○ ○ ○ ○ 1 / 2

T XIB 6 846-50-0 ○/(○)/○ - ○ ● ●

●

(inherently)

○

BCF ● 1 / 2

Notes:

Th e inherent properties for the investigated substances are summarised using key parameters: acute and local

effects, sensitisation, carcinogenicity(C), mutagenic toxicity (M), reproductive toxicity (R), persistence,

bioaccumulation and aquatic toxicity. If data are not available for all parameters or only from non standard

test results a tentative assessment is given (shown in parentheses). The symbols: ● identified potential

h a zard, ○ no identified potential hazard, and – no data available. [] indicate the effects are considered of

m inor significance.

*1 Th e terms refer to different biodegradability tests:

In h erently biodegradable: Not meeting the criteria in an "inherent biodegradability" test

Not r eadily biodegradable: Not meeting the criteria in "ready biodegradability" tests.

*2 ● is ba sed on BCF > 100 or Pow > 3 (BCF prevails ov er Pow where both values exist).

*3 ●● is u sed for very toxic and toxic < 10 mg/L.

*4 Th e following notation is used:


Da ta quality (first number):

1 Da ta summaries from recognised, peer reviewed sources (e.g. EU HVP programme, SIDS, SCHENIR,

NICNAS) or reliable test data.

2 Da ta summaries from not peer reviewed sources, considered reliable with restrictions (e.g. IUCLID).

3 Da ta summaries which do not give sufficient experimental details for the evaluation of the quality.

Da ta completeness (second number):

1 Da ta considered sufficient for classification of CMR effects and according to PBT criteria.

2 Da ta available about the endpoint, but not considered sufficient for classification.

3 Da ta not available or relevant for classification of the endpoint.

A n average score is assigned based on the sum of scores for C, M, R, P, B and T properties as follows: Sum 6-

8 =1, Sum 9-14=2 and Sum 14-18=3

7.4.1 Alternative polymers

Many alternative materials to flexible PVC exist and the subject is complicated. Examples of

alternatives include such diverse materials as linoleum and wood for flooring, woven glass fibre and

paper for wall coverings, and glass for medical appliances.

Focusing on alternative materials with characteristics similar to the characteristics

of flexible PVC, the following flexible polymers are among the principal alternatives to flexible PVC

(Maag et al., 2010):

Ethylene vinyl acetate, EVA;

Low density polyethylene, LDPE;

Poly olefin elastomers (polyethylene and polypropylene elastomers);

Sev eral types of poly urethanes (may in some cases be plasticised with

phthalates);

Isobuty l rubber;

EPDM rubber (may in some cases be plasticised with phthalates);

Silicone rubber.

The ECHA study on DEHP (COWI et al., 2009) concludes that available studies demonstrate that

for many applications of DEHP/PVC, alternative materials exist at similar price. Many of the

materials seem to have equal or better environment, safety and health performance and cost

profiles, but clear conclusions are complicated by the fact that not all aspects of the materials'

lifecycles have been included in the assessments.

Maag et al (2010) concluded that a number of flexible polymers are available which can substitute

for many traditional uses of flexible PVC. Polyethylene (PE), polyolefin elastomers, different

poly urethane (PU) qualities, ethylene vinyl acetate (EVA) and different rubber types are examples

among others. For many flexible PVC uses, also other substitute materials than flexible polymers

exist. The LCA-based, application-focused assessments are few, and often clear-cut conclusions

could not be made. But many materials exist with seemingly equal or better environmental, health

and safety, performance and cost profiles. The a ssessment made Maag et al. (2010) did not allow

for a more detailed analysis of possibilities and limitations in the coverage of alternative flexible

poly mers. For more detailed summaries of the identified studies of alternative materials to flexible

PVC, see (Maag et al. 2010).

7 .5 Historical and future trends

With the increased focus in regulation of phthalates with observed adverse effects, substitution

efforts have taken place over the last two decades. Especially for sensitive purposes like polymer

articles/materials for children, for food contact and for some medical applications, a series of non -

ortho-phthalates has gained more ground, the most dominant substance families being represented

in the description above. From recent COWI studies of phthalates and alternatives, it was observed


that while the traditional phthalates are more dominant in articles imported from Asia, also Chinese

producers are now familiar with providing PVC materials plasticised without the phthalates most

often addressed by regulation; for example so-called “3-P-free” flexible PVC (without DEHP, DBP

and BBP) and “6-P-free” (without DEHP, DBP, BBP, DINP, DIDP and DNOP]).

For general applications of flexible PVC (the dominant plasticiser use), the primary move has been

away from DEHP towards DINP and DIDP (and DPHP), which are closest to “drop-in” alternatives

requiring the least process modifications by manufactures of flexible PVC articles. Please see more

description of this issue in Section 3 .4 on historical trends in use.

7.5.1 Summary and conclusions






supported by a large number of measuring methods designed for this purpose.


functionalities in common with the phthalates family. They are typically branched, quite



The substance family of the plasticiser influences its performance significantly, but some functional

groups in the molecules also influence the performance across families, and plasticisers can

therefore to a certain extent be tailor-made to suit different performance needs. In addition, it is

common to mix plasticisers to achieve desired properties.

Many similar plasticisers have however distinctly different impacts on health and environment, and

are therefore relevant alternatives to phthalates. This is probably primarily due to the fact that

many types of interactions with biological systems are substance specific, and even structure-

specific meaning that substances with identical chemical composition may work differently, if just a

part of the molecule has shifted position from one place to another (as the case is for DEHP and

DEHT).

Most av ailable information on alternatives to primary plasticisers like DINP, DIDP and DPHP

has been reviewed as part of the search for substitutes for the classic general plasticiser DEHP (to

which DINP and to as lesser extend DIDP and DPHP are the key alternatives today). Several

alternatives are however available, both ortho-phtalates (with basic structure similar to DINP,

DIDP and DPHP) and others. The one non-ortho-phthalate with the widest coverage for traditional

DEHP applications is likely its terephthalate counterpart DEHT, which has the same chemical

composition, but a different form, and therefore different environmental characteristics. Otherwise,

no single non-ortho-phthalate plasticiser covers all traditional applications of DEHP (and thus

DINP, its main alternative). Together, however, the reviewed non-ortho-phthalates cover most or

all the key applications. The non-ortho-phthalate alternatives best described include besides DEHT:

DINCH, ASE, DGD, DEGD (in mixtures), COMGHA, DINA, ATBC and GTA. While most of these

have their own environmental issues, many of them are deemed to have overall better

env ironmental performance than DEHP based on the available information. A direct environmental

comparison of DINP, DIDP and DPHP and their alternatives has not been found. Besides

alternative plasticiser use, alternatives to the plasticised materials exist; this has however not been

dealt with in much detail in this review. Some flexible polymer alternatives to flexible PVC include

PU elastomers, various rubber types, silicones, EVA and LDPE, all with different performance

characteristics (note that some rubbers are in some cases plasticised with phthalates).


A wide search of alternatives to the phthalates DEP, DIPP and DMEP has not been possible within

this project. For the use of DEP as a denaturant, many alternatives exist, and DEP is not a part of

the 2013 list of denaturants required used for attaining tax exemptions in EU Member States

(including Denmark). Based on a 2010 review of alternatives to DEHP, DBP and BBP, there are

however clear indications that non-ortho-phthalate alternatives to key applications of DEP, DIPP

and DMEP. Examples include GTA, ATBC, COMGHA, DINCH, DINA, DGD, ASE and a mix with

DEGD as a major component.

Focusing on alternative materials with characteristics similar to the characteristics

of flexible PVC, the following flexible polymers are among the principal alternatives to flexible PVC

(Maag et al., 2010):

Ethylene vinyl acetate, EVA;

Low density polyethylene, LDPE;

Poly olefin elastomers (polyethylene and polypropylene elastomers);

Sev eral types of poly urethanes (may in some cases be plasticised with

phthalates);

Isobuty l rubber;

EPDM rubber (may in some cases be plasticised with phthalates);

Silicone rubber.

Data gaps

Information on direct alternatives to DEP, DIPP and DMEP in different uses.

Direct comparisons of DINP, DIDP and DPHP with available alternatives in relevant uses.


8. Abbreviations and acronyms

ASE Alkylsulphonic phenyl ester

ATBC Acetyltributyl citrate

BBP Butyl benzyl phthalate

BCF Bioconcentration factor

BEHS Benzy l-2ethylhexyl succinate mixture

CLP Classification, Labelling and Packaging Regulation

DEHAtere Di-2-ethylhexyl adipate

DEGD Diethylene glycol dibenzoate

DEHP Bis(2-ethylhexyl)phthalate

DEHT Di(2-ethylhexyl) terephthalate (same as DOTP and DEHTP)

DGD Dipropy lene glycol dibenzoate

DIDP Diisodecy l phthalate

DINCH Diisononylcyclohexane dicarboxylate

DINP Diisononyl phthalate

DNEL Derived No Effect Level

DOA Di-2-ethylhexyl adipate (same as DEHA)

DOTP Di(2-ethylhexyl) terephthalate (same as DEHT)

DPHP Di(2-propylheptyl) phthalate

ECB European Chemicals Bureau

ECHA European Chemicals Agency

ECPI European Council for Plasticisers and Intermediates

EFSA European Food Safety Authority

EPA Env ironmental Protection Agency

EU European Union

GTA Gly cerol triacetate

HELCOM The Baltic Marine Environment Protection Commission (Helsinki Commission)

HMW High Molecular Weight

Kow Octanol/water partitioning coefficient

LOUS List of Undesirable Substances (of the Danish EPA)

LMW Low Molecular Weight

MWWTP Municipal waste water treatment plant

NOAEL No observ able adverse effect level

NOVANA Danish national monitoring and assessment programme

ODS n-Octyl n-decyl succinate mixture

OECD Organisation for Economic Co-operation and Development

OSPAR Conv ention for the Protection of the Marine Environment of the North-East Atlantic

PVC Poly vinylchloride

QSAR Quantitative Structure and Activity Relationship

R&D Research & development

RAR Risk Assessment Report


REACH Registration, Evaluation, Authorisation and Restriction of Chemicals (Regulation EC

1 907/2006)

SCCP Scientific Committee on Consumer Products

SCCNFP Scientific Committee on Cosmetics Products and Non -Food Products intended for

Consumers

SCENIHR The Scientific Committee on Emerging and Newly Identified Health Risks

SPT Association of Danish Cosmetics, Toiletries, Soap and Detergent Industries

SVHC Substance of Very High Concern

TDI Tolerable daily intake

WWTP Waste water treatment plant


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Appendix 1: Background information to chapter 3 on legal fram ework

The following annex provides some background information on subjects addressed in Chapter 3 .

The intention is that the reader less familiar with the legal context may read this concurrently with

chapter 3 .

EU and Danish legislation

Chemicals are regulated via EU and national legislations, the latter often being a national

transposition of EU directives.

There are four main EU legal instruments:

Regulations (DK: Forordninger) are binding in their entirety and directly applicable in all EU

Member States.

Directives (DK: Direktiver) are binding for the EU Member States as to the results to be

achieved. Directives have to be transposed (DK: gennemført) into the national legal framework

within a given timeframe. Directives leave margin for manoeuvering as to the form and means

of implementation. However, there are great differences in the space for manoeuvering

between directives. For example, several directives regulating chemicals previously were rather

specific and often transposed more or less word-by-word into national legislation.

Consequently and to further strengthen a level playing field within the internal market, the

new chemicals policy (REACH) and the new legislation for classification and labelling (CLP)

were implemented as Regulations. In Denmark, Directives are most frequently transposed as

laws (DK: lov e) and statutory orders (DK: bekendtgørelser).

The European Commission has the right and the duty to suggest new legislation in the form of

regulations and directives. New or recast directives and regulations often have transitional periods

for the v arious provisions set-out in the legal text. In the following, we will generally list the latest

piece of EU legal text, even if the provisions identified are not yet fully implem ented. On the other

hand, we will include currently valid Danish legislation, e.g. the implementation of the cosmetics

directive) even if this will be replaced with the new Cosmetic Regulation.

Decisions are fully binding on those to whom they are addressed. Decisions are EU laws

relating to specific cases. They can come from the EU Council (sometimes jointly with the

European Parliament) or the European Commission. In relation to EU chemicals policy,

decisions are e.g. used in relation to inclusion of substances in REACH Annex XVII

(restrictions). This takes place via a so-called comitology procedure involving Member State

representatives. Decisions are also used under the EU ecolabelling Regulation in relation to

establishing ecolabel criteria for specific product groups.

Recommendations and opinions are non-binding, declaratory instruments.

In conformity with the transposed EU directives, Danish legislation regulate to some extent

chemicals via various general or sector specific legislation, most frequently via statutory orders (DK:

bekendtgørelser).

Chemicals legislation

REACH and CLP

The REACH Regulation5 and the CLP Regulation6 are the overarching pieces of EU chemicals

legislation regulating industrial chemicals. The below will briefly summarise the REACH and CLP

5 Regul ation (EC) N o 1 907/2006 concerning the Registration, Ev aluation, Authorisation and Restriction of Chemicals (REACH)

6 Regul ation (EC) N o 1 272/2008 on classification, labelling and packaging of substances and mixtures


prov isions and give an ov erview of 'pipeline' procedures, i.e. procedures which may (or may not)

result in an eventual inclusion under one of the REACH procedures.

(Pre-)Registration

All manufacturers and importers of chemical substance > 1 tonne/year have to register their

chemicals with the European Chemicals Agency (ECHA). Pre-registered chemicals benefit from

tonnage and property dependent staggered dead-lines:

30 Nov ember 2010: Registration of substances manufactured or imported at 1 000 tonnes or

more per year, carcinogenic, mutagenic or toxic to reproduction substances above 1 tonne per

y ear, and substances dangerous to aquatic organisms or the environment above 1 00 tonnes per

y ear.

31 May 2013: Registration of substances manufactured or imported at 100-1000 tonnes per

y ear.

31 May 2018: Registration of substances manufactured or imported at 1 -100 tonnes per year.

Evaluation

A selected number of registrations will be evaluated by ECHA and the EU Member States.

Ev aluation covers assessment of the compliance of individual dossiers (dossier evaluation) and

substance evaluations involving information from all registrations of a given substance to see if

further EU action is needed on that substance, for example as a restriction (substance evaluation).

Authorisation

Authorisation aims at substituting or limiting the manufacturing, import and use of substances of

v ery high concern (SVHC). For substances included in REACH annex XIV, industry has to cease use

of those substance within a given deadline (sunset date) or apply for authorisation for certain

specified uses within an application date.

Restriction

If the authorities assess that that there is a risks to be addressed at the EU level, limitations of the

manufacturing and use of a chemical substance (or substance group) may be implemented.

Restrictions are listed in REACH annex XVII, which has also taken over the restrictions from the

prev ious legislation (Directive 76/769/EEC).

Classification and Labelling

The CLP Regulation implements the United Nations Global Harmonised System (GHS) for

classification and labelling of substances and mixtures of substances into EU legislation. It further

specifies rules for packaging of chemicals.

Two classification and labelling provisions are:

1 . Harmonised classification and labelling for a number of chemical substances. These

classifications are agreed at the EU level and can be found in CLP Annex VI. In addition to newly

agreed harmonised classifications, the annex has taken over the harmonised classifications in

Annex I of the previous Dangerous Substances Directive (67/548/EEC); classifications which have

been 'translated' according to the new classification rules.

2 . Classification and labelling inventory. All manufacturers and importers of chemicals

substances are obliged to classify and label their substances. If no harmonised classification is

av ailable, a self-classification shall be done based on available information according to the

classification criteria in the CLP regulation. As a n ew requirement, these self-classifications should

be notified to ECHA, which in turn publish the classification and labelling inventory based on all


notifications received. There is no tonnage trigger for this obligation. For the purpose of this report,

self-classifications are summarised in Appendix 2 to the main report.

Ongoing activities - pipeline

In addition to listing substance already addressed by the provisions of REACH (pre-registrations,

registrations, substances included in various annexes of REACH and CLP, etc.), the ECHA web-site

also prov ides the opportunity for searching for substances in the pipeline in relation to certain

REACH and CLP prov isions. These will be briefly summarised below:

Community Rolling Action Plan (CoRAP)

The EU member states have the right and duty to conduct REACH substance evaluations. In order

to coordinate this work among Member States and inform the relevant stakeholders of upcoming

substance evaluations, a Community Rolling Action Plan (CoRAP) is developed and publ ished,

indicating by who and when a given substance is expected to be evaluated.

Authorisation process; candidate list, Authorisation list, Annex XIV

Before a substance is included in REACH Annex XIV and thus being subject to Authorisation, it has

to go through the following steps:

1. It has to be identified as a SVHC leading to inclusion in the candidate list7

2. It has to be prioritised and recommended for inclusion in ANNEX XIV (These can be found as

Annex XIV recommendation lists on the ECHA web-site)

3. It has to be included in REACH Annex XIV following a comitology procedure decision

(substances on Annex XIV appear on the Authorisation list on the ECHA web-site).

The candidate list (substances agreed to possess SVHC properties) and the Authorisation list are

published on the ECHA web-site.

Registry of intentions

When EU Member States and ECHA (when required by the European Commission) prepare a

proposal for:

a harmonised classification and labelling,

an identification of a substance as SVHC, or

a restriction.

This is done as a REACH Annex XV proposal.

The 'registry of intentions' gives an overview of intensions in relation to Annex XV dossiers divided

into:

current intentions for submitting an Annex XV dossier,

dossiers submitted, and

withdrawn intentions and withdrawn submissions

for the three types of Annex XV dossiers.

International agreements

7 It shoul d be noted that the candidate list is also used in relation to articles imported to, produced i n or di stributed in the EU .

Cer tain supply chain information is triggered i f the articles contain more than 0.1 % (w /w ) (REACH Article 7.2 f f).


OSPAR Convention

OSPAR is the mechanism by which fifteen Governments of the western coasts and catchments of

Europe, together with the European Community, cooperate to protect the marine environment of

the North-East Atlantic.

Work to implement the OSPAR Convention and its strategies is taken forward through the adoption

of decisions, which are legally binding on the Contracting Parties, recommendations and other

agreements. Decisions and recommendations set out actions to be taken by the Contracting Parties.

These measures are complemented by other agreements setting out:

issues of importance

agreed programmes of monitoring, information collection or other work which the Contracting

Parties commit to carry out.

guidelines or guidance setting out the way that any programme or measure should be

implemented

actions to be taken by the OSPAR Commission on behalf of the Contracting Parties.

HELCOM - Helsinki Convention

The Helsinki Commission, or HELCOM, works to protect the marine environment of the Baltic Sea

from all sources of pollution through intergovernmental co-operation between Denmark, Estonia,

the European Community, Finland, Germany, Latvia, Lithuania, Poland, Russia and Sweden.

HELCOM is the gov erning body of the "Convention on the Protection of the Marine Environment of

the Baltic Sea Area" - more usually known as the Helsinki Convention.

In pursuing this objective and vision the countries have jointly pooled their efforts in

HELCOM, which is works as:

an environmental policy maker for the Baltic Sea area by developing common environmental

objectives and actions;

an environmental focal point providing information about (i) the state of/trends in the marine

env ironment; (ii) the efficiency of measures to protect it and (iii) common initiatives and

positions which can form the basis for decision -making in other international fora;

a body for dev eloping, according to the specific needs of the Baltic Sea, Recommendations of

its own and Recommendations supplementary to measures imposed by other international

organisations;

a supervisory body dedicated to ensuring that HELCOM environmental standards are fully

implemented by all parties throughout the Baltic Sea and its catchment area; and

a co-ordinating body, ascertaining multilateral response in case of major maritime incidents.

Stockholm Convention on Persistent Organic Pollutants (POPs)

The Stockholm Convention on Persistent Organic Pollutants is a global treaty to protect human

health and the environment from chemicals that remain intact in the environment for long periods,

become widely distributed geographically, accumulate in the fatty tissue of humans and wildlife,

and have adverse effects to human health or to the environment. The Convention is administered

by the United Nations Environment Programme and is based in Geneva, Switzerland.

Rotterdam Convention

The objectives of the Rotterdam Convention are:

to promote shared responsibility and cooperative efforts among Parties in the international

trade of certain hazardous chemicals in order to protect human health and the environment

from potential harm;


to contribute to the environmentally sound use of those hazardous chemicals, by facilitating

information exchange about their characteristics, by providing for a national decision -making

process on their import and export and by disseminating these decisions to Parties.

The Convention creates legally binding obligations for the implementation of the Prior

Informed Consent (PIC) procedure. It built on the voluntary PIC procedure, initiated by UNEP

and FAO in 1989 and ceased on 24 February 2006.

The Convention covers pesticides and industrial chemicals that have been banned or severely

restricted for health or environmental reasons by Parties and which have been notified by Parties

for inclusion in the PIC procedure. One notification from each of two specified regions triggers

consideration of addition of a chemical to Annex III of the Convention . Severely hazardous pesticide

formulations that present a risk under conditions of use in developing countries or countries with

economies in transition may also be proposed for inclusion in Annex III.

8.1.1.1 Basel Convention

The Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and their

Disposal was adopted on 22 March 1989 by the Conference of Plenipotentiaries in Basel,

Switzerland, in response to a public outcry following the discovery, in the 1980s, in Africa and other

parts of the developing world of deposits of toxic wastes imported from abroad.

The ov erarching objective of the Basel Convention is to protect human health and the environment

against the adverse effects of hazardous wastes. Its scope of application covers a wide range of

wastes defined as “hazardous wastes” based on their origin and/or composition and their

characteristics, as well as two types of wastes defined as “other wastes” - household waste and

incinerator ash.

The provisions of the Convention center around the following principal aims:

the reduction of hazardous waste generation and the promotion of environmentally sound

management of hazardous wastes, wherever the place of disposal;

the restriction of transboundary movements of hazardous wastes except where it is perceived

to be in accordance with the principles of environmentally sound management; and

a regulatory system applying to cases where transboundary movements are permissible.

Eco-labels

Eco-label schemes are voluntary schemes where industry can apply for the right to use the eco-label

on their products if these fulfil the ecolabelling criteria for that type of product. An EU scheme (the

flower) and various national/regional schemes exist. In this project we have focused on the three

most common schemes encountered on Danish products.

EU flower

The EU ecolabelling Regulation lays out the general rules and conditions for the EU ecolabel; the

flower. Criteria for new product groups are gradually added to the scheme via 'decisions'; e.g. the

Commission Decision of 21 June 2007 establishing the ecological criteria for the award of the

Community eco-label to soaps, shampoos and hair conditioners.

Nordic Swan

The Nordic Swan is a cooperation between Denmark, Iceland, Norway, Sweden and Finland. The

Nordic Ecolabelling Board consists of members from each national Ecolabelling Board and decides

on Nordic criteria requirements for products and services. In Denmark, the practical

implementation of the rules, applications and approval process related to the EU flower and Nordic

Swan is hosted by Ecolabelling Denmark "Miljømærkning Danmark" (http://www.ecolabel.dk/).


New criteria are applicable in Denmark when they are published on the Ecolabelling Denmark’s

website (according to Statutory Order no. 447 of 23/04/2010).


Appendix 2: Danish proposal on criteria for endocrine disruptors

The following criteria for endocrine disruptors are suggested by the Danish Centre on Endocrine

Disrupters (CEHOS, 2012).

Category 1 - Endocrine disrupter

Substances are placed in category 1 when they are known to have produced ED adverse effects in

humans or animal species living in the environment or when there is evidence from animal studies,

possibly supplemented with other information, to provide a strong presumption that the substance

has the capacity to cause ED effects in humans or animals living in the environment. The animal

studies shall provide clear evidence of ED effect in the absence of other toxic effects, or if occurring

together with other toxic effects, the ED effects should be considered not to be a secondary non-

specific consequence of other toxic effects. However, when there is e.g. mechanistic information

that raises doubt about the relevance of the adverse effect for humans or the environment, category

2a may be more appropriate.

Substances can be allocated to this category based on:

Adverse in v ivo effects where an ED mode of action is highly plausible

ED mode of action in v ivo that is clearly linked to adverse in v ivo effects (by e.g. readacross)

Category 2a - Suspected ED

Substances are placed in category 2a when there is some evidence from humans or experimental animals, and

where the evidence is not sufficiently convincing to place the substance in category 1. If for example

limitations in the study (or studies) make the quality of evidence less convincing, category 2a could be more

appropriate. Such effects should be observed in the absence of other toxic effects, or if occurring together

with other toxic effects, the ED effect should be considered not to be a secondary non-specific consequence

of other toxic effects.

Substances can be allocated to this category based on:

Adverse effects in v ivo where an ED mode of action is suspected

ED mode of action in v ivo that is suspected to be linked to adverse effects in v ivo

ED mode of action in v itro combined with toxicokinetic in v ivo data (and relevant non test information such

as read across, chemical categorisation and QSAR predictions)

Category 2b – Substances with indications of ED properties (indicated ED)

Substances are placed in category 2b when there is in v itro/in silico evidence indicating potential for

endocrine disruption in intact organisms. Evidence could also be observed effects in v ivo that could be ED-

mediated.

Strandgade 29

1 401 Copenhagen K, Denmark

Tel.: (+45) 72 54 40 00

www.mst.dk

Survey of selected phthalates

This survey is part of the Danish EPA’s review of the substances on the List of Undesirable Substances

(LOUS). This survey concerns the phthalates DINP, DIDP, DPHP, DEP, DMEP and DIPP. The report

presents information on the use and occurrence of the selected phthalates, internationally and in

Denmark, information on environmental and health effects, releases and fate, exposure and presence in

humans and the environment, on alternatives to the substances, on existing regulation, waste

management and information regarding on-going activities under REACH, among others.

Kortlægning af udvalgte ftalater

Denne kortlægning er et led i Miljøstyrelsens kortlægninger af stofferne på Listen Over Uønskede Stoffer

(LOUS). Denne kortlægning vedrører ftalaterne DINP, DIDP, DPHP, DEP, DMEP and DIPP. Rapporten

indeholder blandt andet en beskrivelse af brugen og forekomsten af de udvalgte ftalater, internationalt

og i Danmark, en beskrivelse af miljø- og sundhedseffekter af stofferne, udslip of skæbne, eksponering og

forekomst i mennesker og miljø, viden om alternativer, eksisterende regulering, affaldsbehandling og

igangværende aktiviteter under REACH.

survey of selected phthalates - miljøstyrelsen6 survey of selected phthalates the process the...

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